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The characteristic chemistry of some organometallic nitrosyl complexes Martin, David Timothy 1984

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THE CHARACTERISTIC CHEMISTRY OF SOME ORGANOMETALLIC NITROSYL COMPLEXES By DAVID TIMOTHY MARTIN B.SC,  UNIVERSITY OF BRITISH COLUMBIA,  1977  M.Sc,  UNIVERSITY OF BRITISH COLUMBIA,  1979  A THESIS SUBMITTED  IN  PARTIAL  FULFILLMENT OF THE REQUIREMENTS DOCTOR OF  FOR THE DEGREE OF PHILOSOPHY in  THE FACULTY OF GRADUATE STUDIES DEPARTMENT OF CHEMISTRY  We a c c e p t  this  to the  t h e s i s as c o n f o r m i n g  required standard  THE UNIVERSITY OF BRITISH COLUMBIA APRIL 1984 © DAVID TIMOTHY MARTIN,  1984  In presenting t h i s thesis i n p a r t i a l f u l f i l m e n t of the requirements for an advanced degree at the University of B r i t i s h Columbia, I agree that the Library s h a l l make i t f r e e l y a v a i l a b l e for reference and study. I further agree that permission for extensive copying of t h i s t h e s i s for scholarly purposes may be granted by the head of my department or by h i s or her representatives. It i s understood that copying or publication of t h i s thesis for f i n a n c i a l gain s h a l l not be allowed without my written permission.  . Department. of c  CHEMISTRY  The University of B r i t i s h Columbia 1956 Main Mall Vancouver, Canada V6T 1Y3 Date  A p r i l 19, 1984  ABSTRACT  Treatment an e q u i m o l a r of  a  of  2  amount  precipitate  (TJ -C H 5  unstable,  characteristic nature. 5  5  donation  air-  it  s u c h as  PPh  or  3  complex  [  5  5  cyclooctene. (e.g.  2  5  Other  P(OPh) . 3  5  5  via  the  either  unsaturated  substrates  ( r ? - C H )W(NO) X 5  5  5  2  (X  green  undergo  the  is  of  the  capable  to  1  H  of  (e.g.  ) ]BF  an  do not  dimerization  Br)  probably  carbocations. with  other  reacts  nucleophiles,  products.  Of  react (e.g.  2,3-dimethyl-2-butene).  anionic  of  (e.g.  transformations incipient  good  results  a  excess  either  also  whose  manner,  isomerization latter  a  type  of  analogous B  of  electrophilic  p o l y m e r i z e d or c o n d e n s e d  = H or  solution  species  its  2  however,  formation  complex  L,  an  exposed  electrophile  dichloromethane-soluble  In 2  formation  is  rapid  )W(NO) ( T ? - C H  or  Phenylethyne  organometallic  5  is  a  1,1-diphenylethene)  occurring  2  5  adducts  Lewis bases,  or  2,3-dimethyl-1-butene),  the  d o m i n a t e d by  olefins,  Allylbenzene)  in  forms  (7? -C H  ( T 7 - C H )W(NO) B F  5  and m o i s t u r e - s e n s i t v e is  with  5  organometallic  with  2  ( T ? - C H )W(NO) C 1  and a b r i g h t  readily  )W(NO) L ] B F „  novel  when  This  of  results  4  AgCl  chemistry  Hence,  [ ( 77 - C H  solution  2  AgBF  of  2  5  thermally  5  of  )W(NO) B F „ .  5  the  a CH C1  X"  greater  The with  to  form  interest  is  the  fact  that  electrophilic derivatives  of  in 5  5  5  their  5  of  formation  5  of 3  the  results  of  or  been e x t e n d e d  to  B,  = C H , 2  also  In  (M  5  5  5  5  2  analogues  complex  5  CH C1 2  cleavage  2  with  results  3  Contrastingly,  readily  with  these  difference  complexes  ]  2  with  2  and  results  2  equimolar  in  the  product not  of  dimers  of  the  acid  [ ( T ? - C H )Cr (NO) 5  5  5  being  ( 77 - C H 5  5  isolable, and the to  by  it  with H  +  are  [ ( 7 ? - C H )M(LO) 5  5  ,  2  may  the  be  derivative  [ (77 -C H )M( LO) 5  ]  2  its  5  2  are  )Cr (NO) BF<,.  but  undergo  5  5  clean  isolated  2  completely  formed  an  } H ] BF „ w h i c h may be  when t r e a t e d  initially  bond.  2 equivalents  propensities C)  and A 1 C 1  +  alkylnitrosyl  spectroscopically  L = N or  o r Mo)  fundamental  )Fe (CO)  5  is  = Cr  analogues.  in  2  contrast,  consume  3  2  a  these  [ (7? -C H  5  The  the  CH Ph  (R  less  to  [ { ( r\ - C H ) Fe (CO)  latter  of  much  carbonyl  3  characterized  terms  Sn)  metal-methyl  of  organometallic  oxidative  or  Ph CH  +  3  point  principal  Fe;  has  Ph C ,  reacts  to  or  Al  2  2  2  required  Cr  (e.g.  )W(NO) R  5  5  HBF„,0(CH )  chemistry.  organic  2  s u c h as H g C l ,  good y i e l d .  This  in  5  reactivity  of  5  ( T ? - C H )M(NO) C H  isoelectronic  amount  linkages  pentamethylcyclopentadienyl  5  of  These the  5  sufficiently  ( 77 - C M e )W(NO) B F „ .  Treatment  in  the  3  between  M-C  main g r o u p e l e m e n t s  chemistry  )Mo(CO) C H  reagents.  the  5  is  2  This  rapid cleavage  (rj -C H  )W(NO) B F „  ( 77 - C H  Treatment electrophiles  5  some new  encompass some o f from  5  cleave  the  complexes.  derivable  5  to  and so p r o d u c e Ph)  ( 77 - C H  5  2  ]  2  (M =  protonation  or  rationalized  in  2  ] H 2  +  adducts.  iv  Table  of Contents  ABSTRACT  i i  T a b l e of C o n t e n t s  iv  List  of F i g u r e s  vi  List  of T a b l e s  Table  vii  of A b b r e v i a t i o n s  viii  Acknowledgements  ix  CHAPTER ONE GENERAL INTRODUCTION  CHAPTER TWO THE CHARACTERISTIC OF  (7j -C H 5  5  5  8  2  Results  Section  10  and D i s c u s s i o n  Preparation  II)  CHEMISTRY  )W(NO) B F „  Experimental  I)  1  of  30  ( r > - C H )W(NO) B F « 5  The c h a r a c t e r i s t i c  5  5  30  2  c h e m i s t r y of  ( T 7 - C H )W(NO) B F „  32  5  5  III) IV)  5  2  The r e l a t e d c h e m i s t r y of  ( TJ - C Me ) W (NO) BF „ 5  5  5  2  The c h e m i s t r y of some r e l a t e d a - l l y l c o m p l e x e s ' .  CHAPTER THREE THE EFFECT OF OF NITROSYL  .  56 59  V  LIGANDS  ON METAL-CARBON a BONDS  Experintental Results  Section  64  and D i s c u s s i o n  70  CHAPTER FOUR PROTONATION V S . CLEAVAGE OF  [ (77 -C H 5  5  Experimental Results I)  5  ) Cr (NO)  III)  OXIDATIVE 2  ]  76  2  Section  77  and D i s c u s s i o n  [(7j -C H )Fe(CO) ]  II)  63  5  5  5  2  5  5  Protonation  2  81  2  [ ( 77 - C H ) C r ( N O ) ] 5  81  82  2  versus  oxidative  cleavage  88  CHAPTER F I V E EPILOGUE  92  REFERENCES AND NOTES  97  APPENDIX  103  vi  List  Figure of  1. The 80-MHz  (T? -C H 5  5  Figure  of  H NMR s p e c t r u m  )W(NO) 7 ? - C H , B F „ 2  5  8  2  Figures  a  in  CD C1 2  36  2  2. The 80-MHz 'H NMR s p e c t r u m  3,3,4,4-tetramethyl-1-phenylcyclobutene  Figure of  1  of  3 . The 80-MHz  (T? -C H 5  5  1  CDC1  3  ..  44  H NMR s p e c t r u m  )W(NO) ( T 7 - C H 3  5  in  3  5  )C1  in C D C 1  3  61  vii  List  T a b l e . I.  Table  "Spectrochemical  II.  He(I)  and H e ( 1 1 )  Analysis  (eV)  (V-C H  )Cr (NO) C H  5  5  Results 2  3  of  Tables  Series"  Valence for  for  7r-Acid Ligands  .  4  Band (T7 -C H 5  5  5  )Fe(CO) C H 2  3  and 95  viii  Table  In thesis Papers  Abbreviations  general  the a b b r e v i a t i o n s  are those  recommended i n t h e  in  addition,  American  Chemical  the f o l l o w i n g  o  degrees  dec  decomposed  E(pa)  aniodic  E(1/2)  half  V  dihapto  2  of  are a l s o  and s y m b o l s u s e d i n "Handbook  Society  f o r A u t h o r s of  Publications".  used:  Celcius  peak  wave  potential  potential  THF  tetrahydrofuran  PPN  bis(triphenylphosphoranediyl)nitrogen(1+)  R  organic  SCE  saturated  FT  Fourier  alkyl  group  calomel  transform  electrode  this  In  ix  Acknowledgements  I  wish  chemistry guidance  to  thank  department throughout  those c o l l e a g u e s includes laboratory  B.W.  Professor occasional  this  with  I  of Peter  I  I  I  expert I  staff  Nurse  as w e l l  and as,  of  the  assistance  am e s p e c i a l l y  worked  most A.D. B.  and  indebted  to  closely.  This  Hunter  whose  Wasssink  whose  from.  would l i k e  Legzdins  enthusiasm.  study.  CR.  shared,  and t e c h n i c a l  their  whom  benefited all  faculty  for  Hames,  space  collaboration Most  the  for  t o e x p r e s s my g r a t i t u d e  his  support,  guidance  to and  X  K e k u l e dreams t h e G r e a t S e r p e n t h o l d i n g i t s own t a i l i n its mouth, the dreaming Serpent which s u r r o u n d s the W o r l d . But t h e m e a n n e s s , t h e c y n i c i s m w i t h w h i c h t h i s dream is to be u s e d . The S e r p e n t t h a t a n n o u n c e s , " T h e W o r l d i s a c l o s e d thing, c y c l i c a l , resonant, e t e r n a l l y - r e t u r n i n g , " is to be delivered into a system whose o n l y a i m i s t o v i o l a t e t h e Cycle. Taking and not giving back, demanding that "productivity" and " e a r n i n g s " keep on i n c r e a s i n g w i t h t i m e , t h e System r e m o v i n g from t h e r e s t of t h e World these vast q u a n t i t i e s of e n e r g y t o keep i t s own t i n y d e s p e r a t e f r a c t i o n showing a p r o f i t : and not o n l y most of h u m a n i t y - most of t h e World, animal, vegetable and m i n e r a l , i s l a i d t o waste i n t h e p r o c e s s . T h e - S y s t e m may or may not u n d e r s t a n d t h a t i t i s o n l y b u y i n g t i m e . And t h a t t i m e i s an a r t i f i c i a l r e s o u r c e t o b e g i n w i t h , of no value to anyone or anything but the System, w h i c h s o o n e r or l a t e r must c r a s h t o i t s d e a t h , when i t s a d d i c t i o n t o e n e r g y has become more t h a n t h e r e s t of t h e World can s u p p l y , d r a g g i n g w i t h i t i n n o c e n t s o u l s a l l along the chain of l i f e . L i v i n g i n s i d e t h e System i s l i k e r i d i n g a c r o s s t h e c o u n t r y i n a bus driven by a maniac bent on suicide . . . Thomas Pynchon  in  "Gravity's  Rainbow"  1  CHAPTER ONE  GENERAL  A chemical their  nitric  metal  states.  of  as  pairs  the  metal  the  negative  important  of  the  compounds a r e important  in  the  transition of  These  vacant  filled  metal  complements  the  is  formal  7r-orbitals  is as  orbitals orbitals  high electron the  accept  to  a-bonding  metals.  ligand  form a arising density  ligands.  Moreover,  structural  catalytic  are  known  many  interest  and o t h e r  a  well  carbon monoxide. Examples  one c a r b o n y l  considerable  industrial,  the  complexes  complexes  be d e l o c a l i z e d o n t o  7r-acid l i g a n d least  these  p o s s e s s i n g vacant  donation. Thus,  atom c a n  compounds w i t h a t all  z e r o or  7r-bonding t h a t  on  delocalized  low-positive,  from  lone-pair  with  sulfides,  these  electrons.  density  or  many of  of  of  isocyanides,  stibines  molecules  is  a wide v a r i e t y  monoxide,  arsines,  metals  [ 1 ] , In  ligands  of  transition with  carbon  various  in  the  The s t a b i l i t y  from the  most  as  s u c h as p y r i d i n e  result  electron  and  of  complexes  such  atoms a r e  oxidation  t y p e of  form  phosphines,  oxide  7t—orbitals  lone  to  molecules  substituted  the  characteristic  ability  neutral  INTRODUCTION  of or  reactions.  The of for  these are  2  Although 1868,  [2]  several  the  metal  centuries  nitrosyl  reasons. not  oxide  literature  this  of  [9,10].  chemical  Secondly,  of  of in  nitrosyl  reviews  most of  the  of  a  some a t t e m p t  has  nitrosyl  the m e t a l ' s  ligand  of  two  main  industry.  If  synthesis  of  Although  of  nitric  applicable  route.  the  metal  into  nitrosyl  the  into  structure  chemistry  the  two  and  main  bonding  been made t o e x p l o i t  oxide on  [3,11,12,13,14],  the  is  efficient  action  research  or  to  [5,6,7,8].  generally  coordinated-nitric  reactivity  c o o r d i n a t i o n s p h e r e has not  the the  of  other  been  fully  of  metal  [15].  complexes,  depend on t h e  linear  a  that  on  the  formed f r o m t h e  not  for  carbon monoxide,  concentrated  [5,6,7,8]  When a t t e m p t i n g  a  the  in  literature  exceeds  o x i d e c o m p l e x e s can be d i v i d e d  investigated  that  [4],  unlike  of  been  t h e major  synthesis  reactivity  groups  as  are  is  Although  effect  has NO  indicate,  nitric  areas  oxide,  b u i l d i n g block  nitrosyls  gas,  known  t h e amount of  c o m p l e x e s has been p r o b l e m a t i c  Consequently,  of  nitric  destroy  some m e t a l  been  c a r b o n y l complexes far  attention  nitrosyl  However,  have  c o m p l e x e s . T h i s c a n be a t t r i b u t e d  a potential  methods t o  complex was p r e p a r e d  complexes  [3].  Firstly,  anything,  carbonyl  nitrosyl  p u b l i s h e d on m e t a l metal  first  nitrosyl  to it  predict is  the  important  formal o x i d a t i o n ligand,  reactivity t o a v o i d any  state  of  the  arguments  metal.  t h e most common f o r m a l i s m  For  regards  3  NO  as  a  nitrosonium  well-studied  indicate This as  the  the  value  as  density  order  an e l e c t r o n  donor,  is  only  in  oxidation only  is  initially  that  is  and t h a t  finally  some c a s e s , number  or  3  electronic  and  it  of  electron  from  leads  not  which  to  an  metal.  true.  For  unsatisfactory Of  chemically  assignment  cation  the  obtained.  distribution.  +3.  complicated.  is  Cr(NO)«  -3 and -4 a r e  physically  to  this  for  where t h i s  [16]  interact  d7r  overly  an  transfers  same 7 r * o r b i t a l  in  Co(NO)  closer  that  +  the  data  first  t o become N O ,  to  bonding s i t u a t i o n s ,  In  course,  important essentially  oxidation  numbers  avoided.  their  requires  more  the  chemistry  extensively  an u n d e r s t a n d i n g o f  and NO. A " s p e c t r o c h e m i c a l been e s t a b l i s h e d to  NO  is  is  c o n s i d e r e d to  that  oxidation  -2,  is  the  metal  this  physical  state  NO i s  that  that,  2  numbers of  While  dislodged is  Fe(CO) (NO) , 2  +2.  in  the  2  and o t h e r  many c a s e s  A c o m p a r i s o n of with  is  are  actual  covalent  returned  satisfactory  thing  the  best  was  there  example,  the  then  usefulness  intuitively However,  of  if  idea  in  an e l e c t r o n Its  The  example, 5  oxidation  obtained  ligand.  For  [Fe(CN) N0] ~,  number  effective  7r* e l e c t r o n  serves  ion,  f o r m a l i s m , Mossbauer  a neutral  its  is  oxidation  that  is  ion.  +  nitroprusside  a s s i g n e d an attractive  (NO )  be t h e  [17]  strongest  nitrosyl  complexes  studied  carbonyl  analogues  relative  series"  (Table  7r-acid.  the  of  I)  for  7r-acidities  71—bonding  and NO i s  The r e l a t i v e  of  CO  ligands  has  generally electron  believed  accepting  Table  I.  "Spectrochemical  NO  PBr CH  CO  As(OCH )  PF  2  9  SbCl AsCl  As(OPh)  3  PClPh  3  7r-Acid  PPh  3  PC'l(OC,H )  3  for  AsPh  3  3  PCI  Series"  2  SPh  3  3  2  As(C H )  3  2  5  P(CH )  2  Ligands  3  3  3  p-CH OC H«NC  P(C H )  PC1 (OC„H )  P(OCH )  0-C H»[P(C H ) ]  PCl Ph  As(NC H  3  2  2  3  9  6  3  5  3  2  5  3  6  1 0  )  3  2  PCNCsH, ) 0  3  5  2  2  5  abilities  of  CO  and  NO  disubstituted derivatives NO  ligands  otherwise  compete  identical  fractional the  set  of  Co(CO) NO  directly  in  for  electron  the  density  below  it  - 1  3  A  1793.2 c m  - 1  in  situations  identical charge it  in  electron electron  relative  from X-ray  series  Mn(CO)(NO)  of 3  of  the  and  is  frequencies  bond s t r e n g t h 7r-acidities  C 1s, N 1s,  g r o u p s b e i n g much s t r o n g e r  CO  higher  However, basis  (or  Support and  spectroscopic  provided  Co(CO) NO, 3  data  NO  for has  studies. of  Fe(CO) (NO) ,  consistent  71—acceptors than  for  force  and 0 1s b i n d i n g e n e r g i e s  Ni(CO)„,  Cr(NO)„  [18].  of  almost  while at  no t h e o r e t i c a l  photoelectron  compounds  power  are  siightly.stronger.  there  measure  CO and NO  accepting  stretching  o r d e r i n g of  measurement  density  NO g r o u p i s  infrared  directly  been d e r i v e d  the  the  that  1658.1  must be remembered t h a t  constants)  The  low  for  3.43%  1909.8  their  densities  assuming t h a t  the  of  the  1717.0 2.40%  Co(CO)(NO)(o-phen)  of  an  4.24%  1956.7  2  in  was c o n c l u d e d  v(NO)  the and  frequencies  4.29% Co(CO)(NO)(PPh )  CO  Using a comparison  A  2044.5 c m  2  which  CO and NO s t r e t c h i n g  u(CO) 3  in  3  compounds t a b u l a t e d  Co(CO)(NO)(PC1 )  been e s t a b l i s h e d u s i n g  environment.  changes  of  have  CO g r o u p s  2  2  w i t h NO [19].  6  What a r e properties found t h a t the  the  of  c o n s e q u e n c e s of  carbonyl  5  5  5  formed by t h e  ligand  organic the  reveal  ligand  exo  is  in  isomer..  the It  the  allyl  position  of  lowest  regiochemistry the  is  polarize  the  coordination  ligands.  influence  other  laboratory  has  (T? -C H 5  5  5  alkyl  derivatives  that  point  It  delineated  these  metal  the  t o NO when  the  t o NO  by  the  the  control  effect  metal  of  arising of  The CO and NO l i g a n d s at  in  nucleophile  electronegativities  nitrosyl  organic  is  the  ligands  intention  some  of  the  tend  centre  the  of  g r o u p s . By way  dicarbonyl  ligands in  to and  of  exert  a  work  from  chemistry groups alkene, of  fragment,  an  metal's  this  work  functional  now be e x t e n d e d t o a s t u d y  cyclopentadienyl  olefinic to  This  s u c h phenomena. P r e v i o u s  of  the  determined  electronic  as  cation  +  the  density.  shows t h a t  2  will  such  nucleophile  trans  been  ligand.  )M(NO) ' (M=Cr,Mo or W)  This  the  distribution  on t h e  sphere.  investigate  believed  effective  coordinated a l l y l  exploitable  of  the  occurs  electron  evidence  has  endo c o n f i r m a t i o n and c i s is  electronic  The above  attack  l i g a n d at  different and n i t r o s y l  the  structures of  It  complexes  3  e x e r t e d by an  carbonyl  at  rj -allyl  addition  that  approaches  from  The  [20].  electronic  ligands?  )Mo(CO) (NO) (1 , 3 - d i m e t h y l a l l y l )  stereospecifically derivatives  different  nitrosyl  nucleophiles attack  (T? -C H  allyl  and  the  to  this of  the  [21-29].  alkyne  and  comparison,  the  ( 77 - C H 5  5  5  )M(CO) , 2  7  is  a common c o n s t i t u e n t  complexes, utility especially  (TJ -C H 5  5  in  5  L=CO  )M(CO)  a large 2  class  the  iron  or  of  organometallic  The m o l e c u l e s have  X .  transition-metal-aided  compare and c o n t r a s t where  of  variant  [30].  the c h e m i s t r y  NO.  X  1  of  organic It  is  widespread synthesis,  now p o s s i b l e  compounds s u c h  as  to 1,  8  CHAPTER TWO  THE  CHARACTERIZATION  The p r e p a r a t i o n cation  of  5  several  [ ( T J - C H ) W (NO) , H ] 5  and  indicated  5  the  adduct.  In  metal-  cation this  of  Further  support  also  the  functions little  a  the b i m e t a l l i c  (7? -C H  further )W(NO)  5  5  5  2  +  ( T J - C , H )W(NO) H ) 5  5  5  precedents  2  bimetallic  reported  [ 2 8 ] . The  these  compounds  viewed  as  a Lewis  formally  18-e"  of e l e c t r o n s  from a  to a vacant  for  donor-acceptor character  the  unit,  was  weak and s o f t that  5  that  time  about  filled  ) W(NO)  5  5  (7j -C H 5  Lewis a c i d s .  concluded  fairly  ( T? -C H  that  unit,  metal-centred  16-e"  it  as  the  formally  c o u l d be s a i d a t  To  the  a pair  adducts with other  studies,  of  be  was p r o v i d e d by t h e f a c t  forms  these  could  1igand-centred o r b i t a l  orbital  interaction  +  view,  2  or  salts  of  5  5  2  properties  ( T J - C H )W(NO) H , p r o v i d e s 5  )W(NO) B F „  5  been  2  chemical  that  acid-base  2  5  has  5  physical  of  OF ( r j - C H  5  5  of  2  +  this  )W(NO) H 2  On t h e b a s i s of ( 77 - C H 5  5  Lewis b a s e . the  acid  5  )W(NO) H 2  However, component  cation. investigate an  the c h a r a c t e r i s t i c  independent  synthesis  and a v a i l a b i l i t y ,  (i.e.  was r e q u i r e d . three  possible  Based  chemistry Free  of of  on c h e m i c a l  syntheses  could  .  9  be  proposed: i)  ( r ? - C H )W(NO) C 1 + A 5  5  5  >  2  A = chloride  ii)  (T} -C H 5  iii)  For  5  2  5  5  5  reasons  chloride  5  )W(NO) *  CIA"  +  2  acceptor  >  +  >  +  convenience,  reaction  5  (TJ -C H )W(NO) 5  5  5  (TJ -C H )W(NO) 5  5  route  was a t t e m p t e d  5  (i)  is  with' A g  + 2  +  CH  +  CO.  + 2  the  most  being  +  4  the  Section  chemicals  u s e d were of  and were e i t h e r  prepared  routinely  purchased  according  ascertained  combination  of  points  uncorrected  are  prepurified  However,  Gallenkamp involving  substrates  H NMR and  nitrogen Melting  grade  or  comparable  commercial  suppliers  IR  analyses the  purity  was  for  using conventional compounds  were  techniques in  for a  commercially verified All  compounds) All  by a  melting (under  using  a  manipulations  performed the  was  melting  in c a p i l l a r i e s  Apparatus.  reagents  or  of  usually  air-sensitive  Point  Purity  and/or  spectroscopies.  and were t a k e n  organometallic  air-sensitive  from  by e l e m e n t a l  l i q u i d organic 1  reagent  to published procedures.  determinations.  obtained  bench  H  5  acceptor.  All  point  +  2  of  This  Experimental  purity  3  (rj -C H )W(NO) (CO)  attractive.  or  )W(NO) C H  5  ion  (T? -C H  on  manipulation  Vacuum  the of  Atmospheres  10  Corporation  Dri-Lab  model  prepurified nitrogen purification  prior  to  internally resonance  were  HE-493  dried  were r e c o r d e d on a  calibrated spectra  with  Dri-Train  according  the  protons  are  reported  Carbon-13  Associates but  on  a  by  downfield  1 3  from  o b t a i n e d at  t h e He/Ne  to  internal of  in  the  parts  NMR  C  to  deaerated  Me„Si.  Elemental  Gas  Perkin  Elmer  Solid  of  2  AgBF„  2  All  instrument magnetic  instrument  CH4B  analyses  were  H  to  mass  solvent in  spectra using  departmental performed  analyses  from Varian  the  reported  by  were c a r r i e d  employing a 8 f t  to  chemical  on a  spectrometer  the  1  or  downfield  recorded  are  by  ppm were the  service Mr. out  x 0.125  P. on a in  Supelcoport.  Solution  was  FT  WP-80  used.  were  4B i n s t u m e n t  a CH C1  band  Proton  million  shifts  column p a c k e d w i t h 3% OV-17 on  Generation  absorption  with reference  chromatographic Sigma  598  5DX  Low-resolution  method  Elmer  tetramethylsilane  per  spectra  chemical  direct-insertion  Borda.  - 1  laser.  solvent  70 eV on an A t l a s  laboratory.  1601 c m  Nicolet  CFT-20 s p e c t r o m e t e r the  Perkin  were r e c o r d e d on a B r u k e r  either  residual  w i t h the  f i l m or  with reference  used,  a  filled  d i s t i l l e d and t h o r o u g h l y  calibrated  a polystyrene  Me„Si.  box  use.  spectrometer  shifts  Solvents  [31],  Infrared spectra  of  dry  and e q u i p p e d w i t h  system.  standard procedures  HE-43-2  added  of  ( T ? - C H )W(NO) B F „ 5  5  to  a  5  green  2  solution  of  11  [32]  (TJ -C H )W(NO) C1 5  5  which  5  2  (0.69  g,  displayed characteristic  and 1650 c m stirred  at  in  - 1  IR  a flocculent  supernatant  nitrosyl  for  1674  whose  cm" .  deposited ambient  an  to  spectrum  This  1  solution  intractable  temperature  the  of  red-brown ( 77 - C H 5  5  were  solid. 2  .used  described  of  red-brown  a  a  was  for  filtered  clear,  5  of  prepurified  evident  slowly  after  at  nitrogen,  30  min.  The  e n h a n c e d by r e m o v a l  the  CH C1 2  according the  green  1754 and  2  an o p e r a t i o n w h i c h a f f o r d e d  generated  darker  s o l i d when s t i r r e d  to  subsequent  of- [ ( r ? - C H )W'(NO) L ] B F , 5  CH C1 2  2  5  5  (L  2  s o l u t i o n of  solution  dichloromethane  min,  and  it  only  of the  solutions  2  this  of  procedure  transformations  below.  colourless  stirred  which time  ^(NO)'s at  5  was  = PPh ,  P(OPh)  3  —  *Z  or  3  '  „)  The a  mixture  S  Consequently, U  2  ( T J - C H )W(NO) B F „  was m a r k e d l y  immediately  Preparation  -—-—  ^ - C s H ,  in vacuo,  )W(NO) B F  5  obtain  i n a atmosphere  decomposition  solvent  1733  mixture  exhibited  the d e c o m p o s i t i o n b e i n g c l e a r l y rate  a b s o r p t i o n s at  precipitate  s o l u t i o n . The f i n a l  IR  mL)  20 m i n , a f t e r  white  through a medium-porosity f r i t solution  (25  2  s p e c t r u m . The r e a c t i o n  room t e m p e r a t u r e  c o n s i s t e d of green  its  in CH C1  2,0 mmol)  briefly whereupon  (10  of  mL).  and was  ( T? -C H 5  5  PPh  3  5  (0,53  The r e s u l t i n g  then p e r m i t t e d  lustrous  )W(NO) 2 B F »  green  to  g,  was a d d e d  2.0  to  mmol)  in  green  solution  was  stand  for  platelets  about  began  10 to  12  crystallize. addition  The  of  Et20  filtration, vacuo  (5  5  5  5  for  Mp ( i n  air)  170°  PPh  lime-green  (s),  C H ), 5  1711  6.40  g,  in  Calcd  When 1.69  (vs)  pure  3.02;  N,4.04.  IR(CH2C12):  v(NO)  ((CD ) CO): 3  6 7.69  2  5.63  (s,  (m,  1H,  15H,  CH2C12).  of  operations  involving  P(OPh)  [ ( r ? - C H )W(NO) {P(OPh) } ] B F „ 5  82%  5  5  2  C  H  2 3  2 0  N BFa0 PW:  C,  5  2  2.90;  N,  3.89.  39.13; H,2.86; IR(CH2C12):  3  J  Hz).  air)  1  5  induced green  5  (5 mL) was  1.0  3  solution  employed  in  the  2  Mp ( i n  of  in  above  The a d d i t i o n the  place  of  Et20  crystallization  of 2  5  for  5  2  decribed  8  9  2  1  a  15H, dec.  (2.00  the  N,  mL,  CH2C12  blue-green  (60  mL)  0.37  g (37%  „ ) ]BF„  to  this yield)  which  was  above.  C, H, N BF„0 W: 3  135°  of  procedure,  5  Calcd  a  /v(NO)  (m,  cyclooctene  [ ( T ? - C H )W(NO) ( T J - C H manner  in  yield.  5H, C H ,  3  3  as  3  5 7.53  solution  Anal.  obtain  4 0 . 2 9 ; H,  ((CD ) CO):  PPh  the  in  .  2  H NMR  resulted.  in  h to  1  solution  isolated  by  and d r i e d  cm" .  15.4 mmol)  bright  collected  0.5  2  H NMR  the  analytically  J=1.2 Hz),  3 9 . 2 6 ; H,  (d,  of  1  3  5  for  a CH2C12  solution  of  C H ,  afforded  Found: C,  1786 6  3  1  sequence  solid  Anal. 3.97.  2  by  dec.  similar of  5  cm" . 5  for  . H I N B C 1 F , 0 2 W : C,  2 3  1694  (vs)  was  x 10 m L ) ,  of  40.29; H,3.06;  (d,5H,  place  (3  Found: C,  6.54  A  ether  room t e m p e r a t u r e  C  completed  solid  3  Calcd  (s),  5  The  yield)  2  C H ), 6  was  )W(NO) ( P P h ) ] B F „ • 0 . 5CH 2 C1  4.00.  1770  with  (69%  Anal. N,  mL).  mm) a t  1  g  [ (rj -C H  (50  washed  x 10~  0.94  crystallization  2  C,  3 0 . 8 6 ; H,  3.78;  N,  13  5.54.  F o u n d : C , 3 0 . 4 6 ; H,  1785  (s),  1674  1704  (vs)  cm" ;  of  5  5  5  (40 mL) The  5  P(OPh)  mixture  slowly  dissolved  light  Celite  ( 3 x 5  under  reduced  lime-green which  5  5  (vide  its  5  5  2  2  s o l u t i o n of  2  4.12  of  in  3.82  CH C1 2  mmol).  whereupon the  2  the  solution and  t h r o u g h a column of slowly  the  3  5  CH C1  1 h,  g,  of  concentrated  precipitation (0.28  g,  of  67% y i e l d )  characteristic  physical  supra).  (10 mL)  2  g,  mixture  became b r i g h t  stirred  at  and  red-brown  filtered  was  induce  ( T ? - C H )W(NO) B F „  2  a  by  3  were t h e n a d d e d ,  filtered  2  identified  of  mL,  (40 mL)  was  to  for  colour  filtrate  pressure  a colourless CH C1 (4.00  Hexanes  1.18  5  properties  The  The  the  P(OPh)  0.58 mmol)  mL,  stirred  and  suspension cm).  (1.00  3  g,  [ ( T ? - C H )W(NO) (P(OPh) } ] B F „  was  Reaction  was  green.  resulting  with  ft  (s),  suspension  (0.29  8  was added n e a t  4  green  )W(NO) 2 ( T ) - C H , „ ) ] B F „  changed to the  8  1776  dec.  1  2  j;(NO)  2  v(HO)  c m " . Mp 104°  2  reaction  solid  2  )W(NO) ( T ? - C H , ) ] B F  S  dark 2  IR(CH C1 ):  5.48.  IR(Nujol m u l l ) :  1  5  a  N,  1050 ( s , b r )  [ ( T? -C H  To [ (T? -C H  cm" .  p(BF)  1  Reaction  (vs)  3.64;  22.8  with Ph CCH 2  ( TJ - C H ) W(NO) B F , 5  5  5  solution mmol).  blue-green  room t e m p e r a t u r e  2  for  precipitate  of  in c o l o u r , the  f o r m e d . The  t h r o u g h a 3 x 5 cm column of  to  1,1-diphenylethene  Initially,  18 h,  was added  2  the  reaction  but w h i l e colour final  Florisil  it  was  lightened mixture  was  supported  on  14  a  medium-porosity  colourless syrup.  filtrate  Ph CCH )  2H,  NMR  J=12  150.4,  this  1.80  2  149.2, 28.79.  147.3,  Reaction  ( T ? - C H )W(NO) B F „ 2  2  10.0  5  solution mL  of  (6.80  18 h a s a red-brown  Florisil  a  distillation  of  filtrate  CH C1  major  as  2  second, small  the  volatile  amount  further. 22H,  1  H  of  the  an  3  2  (ca.  involatile  NMR [ ( C D C 1 ) : 3  3  2  5  on  NMR  60.85, (probe +  mmol) reaction  6 5.27  mixture  The  cm)  three  bp 48  (s,  neat  faded over  ( 3 x 3  the m i x t u r e  which  treated of  filtrate.  2 mL,  2  was  deposited.  afforded  tar  3  gradually  the final  column of Fractional  fractions: (40-41°),  °),  was n o t  and  and gas c h r o m a t o g r a p h i c  (2) (3)  (1) a a  investigated  1H, C H C 1 ) , 2  5  3  283([P-Ph] ).  2  the  q,  (CDC1 ):  61.22,  )W(NO) B F „  solid  by  (AB  spectrum  80.8  which  component o f  (CH ) C=C(CH ) )]  5  colourless  fraction  3.45  5  3  through a short  obtain  2  to  6  +  Initially,  filtered  19H, C H ) ,  ([P-Me] ),  g,  course  based  [33].  2  5  a blue-green colour  was  (26% y i e l d  mass  (r? -C H  acquired  mixture  (30-60°)  with H C C ( C H )CH(CH )  2  2,3-dimethyl-1-butene.  of  (m,  345  +  5  The C H C 1  from l i g h t  1,1,3,-triphenyl-3-indan  Low-resolution  5  viscous  129.1-124.3,  (P ),  the  a  3  9 0 ° ) : m/z 360  with  as  from  left  3H, C H ) . ^ C T H }  temperature  of  solid  properties  (s,  148.7,  solvent  material  5 7.4-7.0  3  Hz, C H ) ,  51.07,  of  spectral  (CDC1 ):  of  reduced p r e s s u r e  identified  characteristic 'H  Removal  a f f o r d e d a white  w h i c h was  2  its  under  Crystallization  petroleum ether 2  frit.  1.64  (s,  analysis  of  2  15  the  second f r a c t i o n  indicated  2,3-dimethyl-2-butene  Polymerization The  CH C1 2  a colourless mmol)  of  CH C1 . 2  in  of  alumina  2  frit.  concentrated  ca.  to  5  by  poly(phenylethyne).  room  grade  became  temperature cm  column  1) s u p p o r t e d on a  red-brown  filtrate  was  mL . and t h e n d i l u t e d w i t h 50 mL of an a u b u r n - c o l o u r e d  filtration It  at  through a 3 x 4  activity  This precipitated  collected  immediately  was s t i r r e d  The  F L  (1.31 mL, 1.02 g , 1 0 . 0  mixture  being f i l t e r e d  medium-porosity  polymer  5  5  It  (Woelm n e u t r a l ,  was a d d e d t o  5  The  2  colour.  30 min b e f o r e  was  ( T ? - C H )W(NO) B F  s o l u t i o n of p h e n y l e t h y n e  for  methanol.  was c a . 4:1 m i x t u r e o f  and d i c h l o r o m e t h a n e .  s o l u t i o n of  2  it  Phenylethyne  i n 5 mL of  green-brown  that  to  yield  was i d e n t i f i e d  by i t s s o l u b i l i t y  and u n r e s o l v e d r e s o n a n c e  solid  0.87  as t h e  g  (85%) of  trans-cisoidal  i n b e n z e n e and by a s i n g l e ,  (ca.  6 7.2)  i n the  which  1  broad  H NMR [ 3 4 ] .  C o n d e n s a t i o n o f P h e n y l e t h y n e and 2 , 3 - D i m e t h y l - 2 - b u t e n e One  half  of  filtered  into  a  (1.10 mL, green  mL, 1.02 g , 0.842  g,  the  ( 77 - C H )W(NO) B F „ 5  precooled 10.0  10.0  mmol)  filtered  alumina  supported  through on  a  5  s o l u t i o n of  2  (1.19  (5 m L ) . The r e s u l t i n g  2  f o r 2 min a t short  was  phenylethyne  2,3-dimethyl-2-butene  and C H C 1  a  solution  2  (-10°)  mmol),  s o l u t i o n was s t i r r e d  quickly  5  -10°  ( 2 x 4  medium-porosity  before  being  cm) column of  frit.  Volatile  16  components  were  pressure  removed  at  from  room  the  filtrate  temperature  1-phenyl-3,3,4,4,-tetramethylcyclobutene as an  vinyl  H  NMR  H) ,  (probe  (CDC1 ):  110°):  CH C1 2  of  (10  2  5  mL,  leave  g,  73%  yield)  5  5  CH C1 2  room t e m p e r a t u r e  for  solution 2  mixture  involatile  residue  Reaction  A solution  of of  ,  +  10.0  added  mmol),  acetonitrile  mass  171  (s,  1H,  spectrum  ([P-Me] ),  156  +  91(C H 7  7  +  ).  and  At  the  a  mixture  [25]  mL,  0.42  solution  was  end  that  be  1690 c m  of  Phenylethyne  under  and  ( T ? - C H )W(NO) B F „ 5  5  the )  - 1  be o n l y  2  of  g,  10.1  stirred  at  time,  a  revealed only  species  through alumina  filtrate  proved to  to  1  2,3-dimethyl-2-butene  spectrum  filtered  5  approximately  to  (0.53  The g r e e n  15 h.  from t h e  (P )  6.28  Phenylethyne  was  1770 and  was  5  +  U  3  (»v(NO):  6  of  )W(NO) (CH CN) ] B F ,  5  removed  Further  186  infrared  containing reaction  mL,  (5 m L ) .  2  5H, C H ) ,  solution containing 2  (1.10  (m,  Acetonitrile  mL)  10.0 mmol),  and  5  in  ( 7 j - C H )W(NO) B F  phenylethyne  were  (1.36  128([P-3Me-CH] ),  Cycloaddition  2,3~Dimethyl-2-butene  [ (r? -C H  m/z", +  Attempted  5  to  Low-resolution  3  143([P-2Me-CH] ),  +  mmol)  7.3  6H, CH .)...  temperature  A  ca.  3  1.30. ( s ,  ([P-2Me] ),  (1.19  reduced  oil. 1  mmol-  under  nitrosyl-  present.  and  The  volatiles  reduced p r e s s u r e .  The  u n r e a c t e d PhCCH.  2,3-Dimethyl-2-butene (ca.  1 mmol)  in  10  mL  1 7  of  CH C1 2  was  2  phenylethyne (6.18  mL,  to  a  CH C1 2  ( 0 . 5 5 mL, 5.0 mmol) 50.0  temperature column  added  mmol).  f o r 30  ( 3 x 4  The  min  cm)  and  was  being  alumina.  mL)  stirred  filtered  Volatile  removed from t h e f i l t r a t e  i n vacuo  NMR s p e c t r o s c o p y  the c h a r a c t e r i s t i c  revealed  unassignable  low-resolution pattern 270  phenyl  mass  and  spectrum  of t h e c y c l o b u t e n e  at  room  oil.  resonances  in a d d i t i o n  the  as peaks  1  H  of  t o some  resonances.  displayed  a  components were  methyl  as w e l l  of  through  to leave a yellow  1-phenyl-3,3,4,4-tetramethylcyclobutene other  solution  2,3-dimethyl-2-butene  mixture  before  of  (5  2  A  fragmentation  a t m/z v a l u e s  of  and 2 5 5 .  A t t e m p t e d C o n d e n s a t i o n of P h e n y l e t h y n e A CH C1  mL)  solution  ( T ? - C H )W(NO) B F „  was  added  (0.55  and c y c l o h e x e n e  2  (10  2  5  5  5  2  mL, 5.0 mmol)  diluted  with  stirred  at  through  a  5  mL  of  of  components from the f i l t r a t e c a . 7.3  3  10H).  Low-resolution  to a mixture  alumina. left  of  ( T? -C H S  5  The  2  in  phenylethyne  mixture  being  Removal  (br m, 5 H , ) ,  )W(NO) B F „  M  of  was  filtered volatile  a viscous o i l .  mass s p e c t r u m  5  0.1  (5.1 mL, 4.1 g , 50 mmol)  (probe  ca.  with  Ph CBr 3  1.7  temperature  m/z 3 6 8 , 2 8 6 , 105, 9 1 , 7 8 .  Reaction  of  f o r 30 min b e f o r e  column  'H NMR ( C D C 1 ) :  approximately  dichloromethane.  room t e m p e r a t u r e short  and C y c l o h e x e n e  (br  m,  100°):  18  The a  CH C1 2  colourless  mmol)  CH C1 2  whereupon  olive-green  the  residue  and the  of  ( T? -C H 5  were  3  cm)  filtrate.  Hexanes  ( 1 0 0 mL)  were  pressure of by  solution  t o induce  bright  was  to  ( T? -C H 5  5  a  the  ( 3 x 40  bright  o f 0.30 g  a  green  filtrate,  [35] which  2  became  through  c o n c e n t r a t e d under  )W(NO) B r  5  ether  to the  2.0  vacuo,  filtered  obtain  added  slowly  in  diethyl  the c r y s t a l l i z a t i o n  green  and  reduced  (33% y i e l d )  was  collected  filtration. Anal.  Calcd  Found:  C,  (s),  1656  15.44;  388,390  of  briefly  cm  2  (5  2  5  a t room This  2  - 1  .  1  H  mL).  most  of t h e [PPN]BF,  H,  1.30; N , 7 . 2 0 .  IR(CH C1 ): 2  NMR  (CDC1 ):  6  3  (probe  j/(NO)  2  1737  6.17 ( s ) .  temperature  80°):  m/z  +  with  2  of  of  was a d d e d  5  5  resulting  operation  [PPN]Br  ( T ? - C H )W(NO) B F  [PPN]Br  temperature  (75  15.44;  ([P-NO] ).  solution  The  C,  7.12.  )W(NO) B F «  solution mL).  2  spectrum  5  5  s  1.38; N,  mass  (7? -C H  CH C1  colourless 2  H,  +  The  2  5  ( P ) , 358,360  Reaction  CH C1  f o r C H N Br0 W:  (vs)  Low-resolution  a  x  immediately  removed  extracts  (  (0.64 g,  3  with  column  resulting  of Ph CBr  extracted  Florisil  the  3  was  to  2  mixture  Solvent  combined  5  solution  reaction  was  )W(NO) B F „ w a s a d d e d  5  ( 1 0 mL)  2  in colour.  resulting mL),  solution  2  5  (1.25 green  before  being  resulted  by-product  2  g,  U  2.0  solution treated  to  mmol) was  in  stirred  with  Et 0  i n the p r e c i p i t a t i o n  as a white  solid  which  2  of was  19  removed by f i l t r a t i o n . Solvent was removed from the f i l t r a t e in  vacuo,  minimum  and  the  amount  transferred  of  remaining CH C1 2  solid  (5  2  mL).  was r e d i s s o l v e d i n a This  solution  by s y r i n g e onto the top of a F l o r i s i l  was  column (3  x 4 cm) made up i n CH C1 . E l u t i o n of the column with CH C1 2  2  2  r e s u l t e d i n the development of a s i n g l e , was  collected.  The  eluate  green  band  was concentrated  under  2  which reduced  pressure to 20 mL before being d i l u t e d with hexanes (40 mL). Further  concentration  crystallization a b r i g h t green  of ( solid  of  this  TJ -C H 5  5  5  solution  )W(NO) B r 2  2  a  2  5  2  s o l u t i o n of (17 -C H )W(NO) BF„ was added 5  s o l u t i o n of [PPN]BH„  5  2  to  V o l a t i l e components were removed  from  mixture  solid  e x t r a c t e d with E t 0 2  to  leave  a  the  final  residue  was  stirred. reaction  which  was  (3 x 20 mL). The e x t r a c t s were taken  under reduced  of a green  solution  warm to room temperature while being  i n vacuo  to  (1.16 g, 2.00 mmol) [36]  (5 mL) at -78°. The r e s u l t i n g green  2  permitted  dryness  (0.51 g, 58% y i e l d ) as  5  2  colourless  in CH C1  the  [PPN]BH„  5  The CH C1  to  (vide supra).  Reaction of ( 7 ? - C H )W(NO) BFn with 5  led  to  pressure t o o b t a i n 0.35 g (56% y i e l d )  s o l i d which was i d e n t i f i e d as (r? -C H )W(NO) H by 5  5  5  2  comparison with an a u t h e n t i c sample [25]. IR (CDCI3):  (CH C1 ): y(NO) 1718 ( s ) , 1632 2  5  6.00  2  (s,  5H,  C5H5),  2.07  (s,  (vs) cm" . 1  1H,  WH).  1  H  NMR  20  Reaction  of  The a  ( T? -C H 5  CH C1 2  The  for  1  Na[BPh„]  h,  during  ( 3 x 6  cm)  frit.  The  The f i n a l  column of bright  to obtain  which  was  6  2  5  2  2.0 mmol)  it  f(NO)  7.42  (m,  5H,  filtered  was of  as  5  5  386  ([P-2NO]*).  356  Reaction  of  The 1 mL o f  ([P-NO] ), +  ( T? -C H 5  5  CH C1 2  2  5  )W(NO) 2 B F „  s o l u t i o n of  a 25% by w e i g h t ,  t o l u e n e m a i n t a i n e d at red-brown  in c o l o u r .  being allowed was  then  326  t o warm t o  filtered  5  was  reduced  Removal pressure  of  2  5  by  2  cm  5  its  - 1  .  1  H  5H,  NMR  C H ). 5  80°):  5  m/z  3  )W(NO) B F „  s t i r r e d at  a column  solvent  solid  )W(NO) P h  (s,  2  -78°  for  produced a v i s c o u s  (C H ) A1 2  5  3  ( 3 x 6  this  cm)  of  green o i l .  in  before mixture alumina  a bright filtrate  to  became  5 min  The f i n a l  to o b t a i n  from  was added  the m i x t u r e  room t e m p e r a t u r e .  through  in  (C H ) A1  Immediately,  s u p p o r t e d on a m e d i u m - p o r o s i t y f r i t filtrate.  green  c o l o u r l e s s s o l u t i o n of  -78°. It  5  to dryness  temperature  with  (7j -C H  5  5.06  (probe  +  short  medium-porosity  (vs)  L o w - r e s o l u t i o n mass s p e c t r u m (P ),  red-brown  [22],  1634 5  (35  2  through a  taken  (7j -C H  to  temperature  a  a bright  C H ), 6  2  developed  filtrate  1720 ( s ) ,  CH C1  room  s u p p o r t e d on a  identified  was added  4  in  s t i r r e d at  m i x t u r e was  green  t  spectroscopic properties 2  6  6  g,  0.38 g (48% y i e l d )  (CH C1 ):  (C D ):  5  time  alumina  readily  characteristic IR  5  (0.69  which  Na[BPh ]  ( r ? - C H )W(NO) B F  r e s u l t i n g m i x t u r e was  colouration.  vacuo  with  2  5  s o l u t i o n of  2  s u s p e n s i o n of  mL).  )W(NO) B F „  5  green under  Sublimation  21  of  this  residue  ( 4 0 ° , 5 x 1 0 ~ mm) o n t o a w a t e r - c o o l e d  a f f o r d e d 0.11 g (16% y i e l d ) analytically Anal. Found: (s),  pure,  7  C,25.05;.  1.96  (m,  ( T} -C H  H,  1 0  5  green  N 0 W: 2  1  2  6  55°):  m/z  338  as  5  an  H, 2 . 9 8 ; N, 8 . 2 9 . 2  8 4.98  6  2  (CH C1 ):  Low-resolution  5  2  solid.  2 . 9 7 ; N, 8 . 3 1 . IR  C H ).  5  C, 24.87;  2  1  )W(NO) C H  5  c m " . H NMR ( C D ) :  5H,  temperature  of  crystalline,  Calcd for C H  1619 ( v s )  probe  3  (P ),  (s,  5H,  C H ), 5  mass s p e c t r u m 308  +  v(NO) 1707  2  5  (probe  ([P-NO] ),  278  +  ([P-2NO] ). +  Preparation A mmol)  of  of  benzyl chloride  i n THF was added t o a m i x t u r e g,  stirred  41.1  mmol)  and  f o r 2 h without  temperature.  THF  ( 1 . 7 3 mL, 2 . 5 3 g , 2 0 . 0 of  At t h e end of t h i s  time,  (PhCH ) SnCl 2  magnesium  (100  being allowed  (15 mL) s o l u t i o n of  [37], h  2  solution  (1.00  THF  (PhCH )„Sn  m L ) . The m i x t u r e was to it  warm  and t h e r e s u l t i n g m i x t u r e was s t i r r e d  before  mL).  The  anhydrous  being  hydrolyzed  or.ganic CaCl  2  phase  with c o l d ,  was  before  vacuo.  The r e m a i n i n g c o l o u r l e s s  light  (30-60°)  (PhCH ) Sn 2  u  Anal. C,69.75;  petroleum  ether  at  C,  H,  5.91.  'H  Sn:  NMR  reflux  and  -78°  Calcd for C  2 8  10.0  mmol) f o r 18  dried  69.60;  (CDC1 ): 3  (50 over  s y r u p was c r y s t a l l i z e d  as a white  H  at  with a  was removed f r o m i t  ( 2 . 3 3 g , 48% y i e l d ) 2 B  g,  room  d e i o n i z e d water  separated  the s o l v e n t  above  was t r e a t e d  (4.27  3  turnings  to  in  from  obtain  pure  solid. H,  5.84.  6 7.24-7.05  Found: (m, 20H,  22  C H ), 6  2.21  5  Reaction  of  2  for  2  with  5  5  5  2  2  colPurless  CH C1  8 H , C H ) . Mp 4 2 ° .  ( T } - C H )W(NO) B F „  CH C1  The a  (s,  2  s o l u t i o n of solution  (T? -C H  (PhCH )„Sn 2  5  5  of  5  )W(NO)  (PhCH ) Sn 2  90 min d u r i n g w h i c h  the  colour  The  final  Florisil hexanes  mixture  solution  was f i l t e r e d  of  room  an o l i v e - g r e e n  filtrate.  and slow  5  collected  by  Anal.  2  2  for  C  1 2  H  l 2  N 0 W: 2  C,  2  (s),  c m " . H NMR ( C D C 1 3 ) :  1626  (vs)  5.81  (s,  Low-resolution (P ),  Solid slurry  CH C1 2  2  mass  5H,  of  5  3.17  5  (probe +  3 . 0 2 ; N,  5 7.30-7.07 (s,  91  JV(NO)  2  2H,  temperature  340 ( [ P - 2 N O ] ) ,  (C H 7  7  (m,  CH ). 2  7 5 ° ) : m/z +  ).  ( T 7 - C H )W(NO) O S Q C H C H 3 5  5  5  2  ( T ? - C H )W(NO) C1 5  5  of  silver  (25  mL).  d u r i n g which  C H ),  H,  2  1  spectrum +  Preparation  a  1  370 ( [ P - N O ] ) ,  +  was  IR(CH C1 ):  1714  400  which  36.02;  H, 3 . 1 1 ; N, 6 . 7 5 .  5  under  of 0 . 1 4 g (18%  solid  Found: C, 36.68;  6  of  filtration. Calcd  C H ),  olive-green.  The a d d i t i o n  7.00.  5H,  formed and  concentration  ( T J - C H )W(NO) C H P h as a g r e e n 5  in  temperature  became  induced the c r y s t a l l i z a t i o n  5  to.  t h r o u g h a 3 x 4 cm column of  (50 mL) t o t h e f i l t r a t e pressure  at  a brown p r e c i p i t a t e  of t h e s u p e r n a t a n t  to obtain  reduced yield)  time  was a d d e d  a  ( 0 . 9 6 g , 2.0 mmol)  a  (5 m L ) . The m i x t u r e was s t i r r e d  2  BF  2  time  5  2  2  6  (0.69 g,  p-toluenesulfonate The  reaction  its physical  4  2.0 mmol)  was a d d e d t o  ( 0 . 5 6 g , 2.0 mmol)  mixture  appearance  was s t i r r e d did  not  in  for 3 h change.  23  The  final  column  mixture  of  Celite  Concentration  of  formation  a  of  filtration, 10 ~  (T? -C H 5  5  of  5  its  )W(NO)  IR,  1  solid  2  6  (3  5 7.41  readily  g,  70% y i e l d )  and mass s p e c t r a  1737 ( s ) ,  i;(NO) (m,  4H, C H ) , 6  5  -78°  5  of  5  s  5  rapidly  was  2  2.0  g of  occurred,  spectroscopy, absorptions  and due  disappeared.  The  2  and d r i e d  (5 x  identified  as  by c o m p a r i s o n d i s p l a y e d by  (vs)  (s,  cm  - 1  .  5H, C H ) , 5  (probe  5  'H  NMR  2.70  (s,  temperature  165  solution  of  C1  g,  ClNO i n and  the to  the  to a p p r o x i m a t e l y  2  mL  of  reaction was  in  CH C1 2  2  was  at  2  of  ClNO  [39]).  monitored  organometallic  being  the  by  then  in IR  had  permitted  concentrated  s o l u t i o n was  Gas  carbonyl  reactant  m i x t u r e was  10 mL. T h i s  2  mixture darkened  added u n t i l  before  CH C1  solution  2  reaction  reaction  room t e m p e r a t u r e  [38]  CH C1  30  ClNO  final  a  the  the  orange  1 1 . 6 mmol)  dropwise  The p r o g r e s s of  t o warm t o  by  [25],  1650  stirred,  NO ( 4 . 6 8  added  (containing  colour.  ( r\ -C Me ) W(NO)  )W(CO)  evolution  collected  with those  6.15  a  the  +  a  (i7 -C Me  x 10 m L ) ,  in  (P ).  Preparation To  was  cm) frit.  resulted  was  (0.67  3  vacuo  which  solid  OS0 C H«CH  2  m/z 480  vacuo  green  ( 3 x 4  medium-porosity  in  L o w - r e s o l u t i o n mass s p e c t r u m  3  5  filtrate  a  sample p r e p a r e d p r e v i o u s l y 2  3  °):  2  through a short  on  the  powdery  (CH C1 ):  (CDC1 ): CH ).  supported  H NMR,  an a u t h e n t i c IR  filtered  washed w i t h h e x a n e s  mm). The  3  was  in  transferred  24  via  syringe  made  up  o n t o t h e t o p of a 3 x 5 cm  in  CH C1 . 2  2  produced a green hexanes  yield) by  of  which  was  band  (100  concentration  Elution  mL)  under  to  the  column  the  column  reduced p r e s s u r e ,  Florisil  with  collected.  eluate,  of the green c r y s t a l l i n e  of  2  Addition  followed  w h i c h was  2  of  by  slow  g  (52%  a f f o r d e d 2.48  product  CH C1  collected  filtration. Anal.  6.76.  Calcd for C, H 0  Found:  1705 ( s ) ,  C,  414  28.97;  1625 ( v s )  Low-resolution  N C10 W: 2  H, 3 . 7 0 ; N , 6 . 6 8 .  cm" . 1  mass  C, 28.97;  2  1  H  NMR  spectrum  H, 2  5  3  2  2.03  temperature  N,  v(HO)  IR(CH C1 ):  (CDC1 ):  (probe  3.64;  (s).  9 5 ° ) : m/z  ( P ) . Mp 1 8 8 ° . +  Preparation A  of  ( 7 ? - C M e )W(NO) H 5  green  5  5  5  2  with  (25  (0.73  2  dropwise  5  toluene  ( 77 - C M e )W(NO) C 1 5  2 5  a  g,  (0.6  diluted  change  reaction  2  to  2  3  10 m L ) . mixture  2  No  was i m m e d i a t e l y  30 min t o e n s u r e  complete  reaction  of  in  had been a d d e d ,  b e i n g warmed  mixture  was  at  containing  - 7 8 ° was  toluene  mL  aluminum r e a g e n t  and w i t h o u t  solution  1.76 mmol)  colourless  Na[A1H (OCH CH OCH ) ] 2  mL)  solution  a 70% t o l u e n e the  treated  solution  appearance  apparent.  After  the mixture  of  of  all  the  of the  was s t i r r e d  for  reaction.  At t h e end o f t h a t  time,  to  temperature,  final  room  quickly  filtered  the  t h r o u g h a column of  Florisil  ( 3 x 5 cm) s u p p o r t e d on a m e d i u m - p o r o s i t y  frit.  filtrate  was t a k e n  resulting  to dryness  in vacuo,  and  the  The  25  residue  was  crystallized  from  ( T ? - C M e )W(NO) H a s w e l l - f o r m e d , 5  5  5  hexanes  green  2  to  crystals  obtain (0.42  g,  63% y i e l d . ) . Anal.  Calcd  for  7.39.  Found: C, 31.36;  1894  (w)  (CDC1 ):  cm" ; 1  Low-resolution 380  (P ).  Preparation  of  mmol)  green in  The  solution  slowly  mixture 3  31.60;  1626  2.17  (vs)  (s,  (probe  2  AgBF„  H, 4 . 2 4 ; N, t-(WH)  c m " . ' H NMR 1  15H,  C (CH ) ). 5  temperature  3  5  3 5 ° ) : m/z  of  1.0 mmol)  (7? -C Me )W(NO) C 1 5  mL).  (0.27  3  (0.20 g, 5  5  1.0  into  mmol)  of  reduced  a to  (25 mL) were a d d e d , under  white  was s t i r r e d  filtered g,  was a d d e d t o a (0.42  2  A flocculent  mixture  was  concentrated  5  2  30  a CH C1 2  obtain  2  min. (5 mL)  a  green  and t h e s o l u t i o n was  pressure  5  1.0  precipitate  for  to  [ ( 7 } - C M e )W(NO) ( P P h ) ] B F 5  g,  induce  the  as a  green  solution  of  3  U  ( 0 . 4 6 g , 63% y i e l d ) . B.  ( r ? - C M e )W(NO) H 5  5  2  added s o l i d solution 1.0  W-H),  the r e a c t i o n  Hexanes  Method 5  (s),  5  (20  2  crystallization solid  C,  2  1704  5  solution  of PPh  solution.  2  spectrum  5  2  final  N 0 W:  [ ( 7 ? - C M e )W(NO) ( P P h ) ] B F „  CH C1  formed w h i l e  l 6  (dec).  Method A . S o l i d stirred  H  H, 4 . 2 7 ; N, 7 . 2 4 . I R ( h e x a n e s ) :  1H,  mass  Mp 7 7 °  +  1 0  (NO)  p  5 3.17 ( s ,  3  C  To (0.38  Ph CBF„ 3  was s t i r r e d  mmol)  a  stirred g,  (0.33 for c a .  green  1.0 mmol) g,  1.0  in CH C1 2  mmol).  15 m i n , whereupon  was a d d e d . The s u b s e q u e n t  addition  2  (20 mL) was  The PPh  resulting 3  (0.27 g,  of h e x a n e s  (15  26  mL)  and slow  led  to  c o n c e n t r a t i o n of  the  precipitation  the  final  of  solution  0.61  g  N BF,,0 PW:  C,  (84%  in  vacuo  yield)  of  the  4.15;  N,  product complex. Anal. 3.85. 1744  Found: (s), 3  C,  C  3 0  2  2  H,  cm" . 1  "J=0.5 H z ) ,  5  H  2 8  45.73;  1673 ( v s )  C (CH ) , 5  Calcd for  1  4 . 2 1 ; H,  46.18;  3.77.  IR(CH C1 ): 2  H NMR ( ( C D ) C O ) : 3  7.72  (m,  15H, C H ) .  Mp ( i n  5  y(NO)  2  5 2.05  2  6  H,  (d,  15H,  air)  144°  dec.  Preparation A AgBF  (0.20  the  2  to in  a  5  mmol)  10"  a  6.86.  C (CH ) ), 3  5  5  5  s  generated (0.41  2  supra).  This 5  acquired  cm),  was  and t h e  Sublimation  of  the  resulted  in  upon warming a  t h r o u g h an was  residue  onto a w a t e r - c o o l e d probe a f f o r d e d the solid  Calcd for  1 2  H  35.31;  1606 (vs) 1.97  C  (0.02  1  5%  N O W: 2  H,  cm" . (q,  2 0  g,  5.02; 1  N,  35.31;  6.68.  H NMR ( C D C l ) : 3  2H, C H , J = 7 . 3 H z ) , 2  taken (75°,  5  product  yield).  C,  2  to  green-brown  filtrate oily  was 1.0  filtered  green  1.0  g,  3  red s o l u t i o n which,  mixture  g,  ( C H ) A 1 (0.11 2  from  solution  -78°. This operation  gradually  ( 3 x 6  Found: C,  1685 ( s ) ,  at  was  U  ( T? -C Me )W(NO) C 1  s o l u t i o n of  final  complex as a green Anal.  5  2  (vide  dark  in vacuo.  mm)  2  5  and  (2 mL)  The  column  3  5  colourless  colouration.  5  5  (10 ML)  2  toluene  to dryness  2  ( 7 j - C M e )W(NO) B F  temperature,  alumina  5  of  1.0  formation  room  x  5  g,  in CH C1  added mmol)  ( T ? - C M e )W(NO) C H  solution  fl  mmol)  of  H,  4.94;  N,  IR(hexanes):  v{HO)  5  15H,  1.95  1.27  (t,  (s, 3H,  CH ). 3  27  L o w - r e s o l u t i o n mass s p e c t r u m 408  (probe  temperature  55°):  m/z  (P ). +  Preparation An  of  [ ( r ? - C H )W(NO) ( r ? - C H ) (NCCH ) ] B F , 5  orange  4 . 5 mmol)  [40]  in 2  3  (100  mL)  2  t h e c o l o u r was b l e a c h e d precipitate  C, H , N B F „ O W : 0  3  (d,  1H, H  7.3  Hz),  3 1  ,  J  Preparation  mmol o f  3  .  1  2  of  1640  j/(NO)  5H, C H ) , 5  (m,  (87%  3.97  2H,  H  1  yield) yellow  IR(Nujol  cm  of powder.  - 1  mull):  . H NMR o f  f  of  d,  1H, H  H  ),  1.96  1 2  3 2  ,  v  major  1  2  (d  1  solid  6 . 1 7 (m, 1H, H , ) ,  5  to  4.18  J32-21  (s,  free  ( T? -C H ) W(NO) ( T? - C H ) C l 5  5  3  (7) -C H 5  3  3  5  yellow  )W(N0) ( r j - C H 5  ;  12.9 H z ) ,  3  taken  [41] Mp 157° d e c .  a pale 5  - 1  6 6.17 ( s ,  2.73-2.52  acetonitrile)  5  cm  The  C , 2 6 . 8 2 ; H , 2 . 9 3 ; N,  2  2301,  5  was  3  5  (CN)  3  formed.  g  F o u n d : C , 2 6 . 6 4 ; H, 2 . 8 6 ; N, 6 . 0 6 .  isomer(CD CN):  from t h e  provided  for  2326  stirred  of the remaining  0.75  with  of the mixture  filtrate  6.25.  [ (TJ -C H  m i x t u r e was  Recrystallization  3  Calcd  5  treated  3  5  Anal.  To  was  )W(NO) ( T ? - C H ) (NCCH ) ] B F „ as a p a l e  5  5  5  ( 3 x 3 c m ) , and t h e  CH C1 -Et 0  [ (TJ -C H  5  The r e a c t i o n  time  (2.0 g,  3  5  of A g B F „ .  vacuo.  2  3  s o l i d was removed by f i l t r a t i o n  through C e l i t e  from  5  l i q u i d and an o f f - w h i t e  precipitated  dryness  3  ( rj -C H )W(NO) ( T ? - C H ) I  in a c e t o n i t r i l e  1 h, d u r i n g which  supernatant  3  5  s o l u t i o n of  0 . 8 9 g ( 4 . 5 mmol) for  5  acetonitrile 5  ) (NCCH ) ] B F 3  )W(NO) ( T ? - C H 3  5  3  3  5  )I  a  in  s  (50  mL)  solution  (generated the  manner  from  of 3.98  described  28  above)  was a d d e d an e x c e s s o f  The r e s u l t i n g 15  h,  the  Volatiles in  a  colour  of  were t h e n  vacuo,  10 mL of  s u s p e n s i o n was  2  Hexanes  s o l u t i o n was These  Celite  (30  mL)  slowly  5  3  5  orange  Found: 1  H  1  ,  26.91;  H NMR 4.67  5  3 2  Calcd for  C,  C H ), 5  J  1 2 2 1  (d,  reduced  2.83; 6 ca.  1H, H J  3 2  Hz,  C,  3 1  ,  J  3 1  3.90.  6.29  (m,  _  2 1  of  as  a  pale  Hz),  J, _ i=2.9  2.84;  N,  3.94.  Preparation  of  IR(CH C1 :) 2  Hz), 2.45  (d  for  Anal. C,  of  2.12  mass  d of  d,  5H, d,  1H,  d,  1H,  1H,  spectrum  H  1 1 r  (probe  Mp 149°  +  1630  (s,  (d of  (d of  325 ( P - N O ) .  +  WNO)  5.99  3.84  dec.  ( T ? - C H )W(NO) ( T ? - C H )Br - . 5  3  5  s  5  3  T h i s compound was p r e p a r e d by a r o u t e descrbed  2  2  Hz),  1  H,  1H, H , ) ,  =14.2  _12=3.8 2  27.03;  N,  m/z 355 ( P ) ,  Found:  the  pressure.  yield)  110°):  2  under  and  83%  temperature  _  filtrate,  g,  Low-resolution  n  medium-porosity  crystallization  Hz).  J  the  3 x  through  the  1 0  H,  Hz,  =6.4  !=9.0  8  3  3  2  into  in  C H NC10W:  (CDC1 ):  J 2_2i=6.9  H, ,  (1.17  5  mixture  were f i l t e r e d a  for  solid.  Anal.  cm" .  3  mmol).  intensifying.  reaction  s u p p o r t e d on  resulted  13.4  was e x t r a c t e d  were added t o  ( 7 ? - C H )W(NO) ( r ? - C H )C1  g,  room t e m p e r a t u r e  final  residue  concentrated  manipulations  5  at  The c o m b i n e d e x t r a c t s  2  (1.00  solution gradually  remaining  3 x 4 cm column o f  frit.  stirred  removed, from t h e  and t h e  CH C1 .  the  s o l i d KC1  c h l o r o complex Calcd for  23.88;  in  the  C H NBrOW: 8  H,2.46;  1 0  N,  3.41.  analogous  preceeding C,  24.03;  H, 2  that  section.  IR(CH C1 ): 2  to  2.52;  N,3.41.  *>(NO)  1634  29  cm  1  .  L o w - r e s o l u t i o n mass s p e c t r u m ( p r o b e  m/z 401  (P ), +  371  ([P-NO] ). +  temperature  105°):  30  Results  and D i s c u s s i o n  I)  Preparation  dichloromethane  of  ( T? -C H 5  solution  w i t h an e q u i m o l a r  amount  rapidly  The  forms.  )W(NO) B F . ' '  5  of  5  2  When  t  ( T ? - C H )W(NO) C1  is  5  5  5  of A g B F ,  a  u  2  precipitate  chloride-abstraction  a  treated of  AgCl  reaction  which  occurs,i.e.,  (V-C H 5  5  )W(NO) C1 + A g B F „  > ( T J - C H )W(NO) B F „ 5  2  5  5  2  +  AgCl (1)  is  complete  solution  in  20 min a t  IR  absorptions  at  organometallic  The  1733  cm"" c h a r a c t e r i s t i c  and  reagent new  bands  assigned  as  the  y(NO)'s  1 is effected  proton  'H  resonance  replaced 6.27).]  by  cleanly The  slower  at  5  5  5  of  5  2  ( T? -C H 5  5  5  2  at  facile  2  (X  = Br  in a stepwise  or  and which 2  at  manner  can e a s i l y  5  6.16  lower in  be  and A g ( l )  [42,43],  being  field  which  The r e l a t e d  fashion  [When  cyclopentadienyl  slightly  I)  are  c a n be  )W(NO) BF„.  5  the  i s noteworthy.  )Fe( CO) X  - 1  i t s progress  )W(NO) C1  by a new s i n g l e t  and p r o c e e d  intensity  spectroscopy,  proceeds  (T? -C H  in  5  2  of t h e  1  ( T? -C H  in CD C1 ,  NMR  nitrosyl-stretching  1754 and 1674 c m of  relatively  transformation between  1650  diminish  by  monitored  a s m o n i t o r e d by  spectroscopy.  replaced  reaction  room t e m p e r a t u r e  (6  this  reactions salts  e.g.,  are  31  ( r ? - C H )Fe(CO) I 5  5  5  + 0.5  2  AgBF,,  (2) 0.5  [ { ( T 7 - C H ) F e ( C O ) } I ]BF 5  5  5  2  2  + 0.5  tt  Agl  0.5 A g B F „  (TJ -C H  )Fe(CO) B F „  5  5  the  second s t e p not  The  isoelectronic  intermediate recently  (T? -C H 5  5  5  occurring u n t i l chromium  the  haiide-bridged,  2  5  S0  However,  spectroscopic  reaction  1  formation  provides of  2  5  )Cr (NO) 5  5  monitoring evidence  [ { ( r ? - C H )W(NO) } 5  of  the  cation  has  also  manner  (S0  completed.  [44],i.e.,  ) ]AsF  2  >  6  + [{(rj -C H )Cr(NO) } Cl]AsF .  no 5  2  is  analogue  bimetallic  been s y n t h e s i z e d i n a s i m i l a r  )Cr (NO) C 1 + [ ( T ? - C H  first  nitrosyl  5  5  + 0.5 A g l ,  2  5  2  5  2  of  the  for 2  (3)  6  progress  even  C1 ] B F „  2  the  of  transient  during  this  conversion. Removal  by  filtration  reaction  1 produces a b r i g h t  desired  organometallic  of  the  green,  product  AgCl byproduct CH C1 2  which  in  of  the  fumes p r o f u s e l y  when  2  solution  formed  32  exposed to the atmosphere. also  thermally  Regrettably,  unstable,  depositing  d e c o m p o s i t i o n p r o d u c t s when m a i n t a i n e d of  prepurified  nitrogen  ( 7 ? - C H )W(NO) B F i , 5  5  5  determine  i t s . exact  currently  known  (T? -C H )Cr(NO) 5  5  2  be i s o l a t e d  identity.  about  F P F  such  [45],  5  5  complex p o s s e s s e s  monodentate  (T? -C H 5  5  exist  in  CH C1 2  coordinatively  2  5  -  Alternatively,  as  2  discrete  unsaturated  incorporating  a  coordination  sphere.  5  of  In  Consequently,  given  )W(CO) Y  (Y  3  is  5  5  as  = FBF  that  ligated 5  in  2  pairs  or  3  ( 77 - C H )W(NO) B F  event,  to  what  is likely  weakly  solvent  any  state  complexes  organometallic  molecule  atmosphere  in the s o l i d  ion  is  insoluble  an  [43], i t  3  the B F , , anion  fashion.  under  related  5  5  only  Nevertheless,  [ 4 6 ] , and ( T 7 - C H ) F e ( C O ) F B F  FPF )  the  5  solution  a t room t e m p e r a t u r e .  cannot  2  this  f t  may  with  cation  a  the  possibly  into  the  metal's  the  characteristic  r  chemistry  o f t h e compound i n  electrophi1ic  nature,  nucleophiles.it 16-electron 11) (a) ( 775  is  dominated  i t s reactions  though  5  5  5  with 2  as  2  it  were  by  with the  its  various formally  [ ( T ? - C H )W(NO) ] .  - C H )W(NO) B F „  ligands  as 2  The c h a r a c t e r i s t i c  5  2  and d u r i n g  behaves  Reaction 5  CH C1  in  strong readily  Equation  t r iphenylphosphi te)'.  +  chemistry Lewis forms  of  ( 7 ? - C H )W(NO)  bases. adducts  5  5  5  2  BF„.  Not s u r p r i s i n g l y , with  good  donor  4 where L = t r i p h e n y l p h o s p h i n e  or  33  (T7 -C H )W(NO) BF  + L  5  5  The  5  2  resulting  salts  organometallic previously the  p r e p a r e d as  indistinguishable  in  PF "  salts  6  the  5  3  a b s o r p t i o n s at  cm" ,  which are  respectively,  energy  than  solvent. in  not  CH C1 2  metal  than  the  consistent to  2  cations. the  exhibited  Significantly,  energy  is  those  they  HNO)'s  w i t h the  form d i s c r e t e  or  are of  complexes  (b)  in d -acetone 6  Reactions  introduction  of  an  even  1711  higher  in  the  2  cm  same higher  - 1  fact  2  5  solvated,  to  of  [ ( TJ -C H 5  5  course,  density the  H NMR the  olefins  of  spectra expected  and  cyclooctene  5  solely  ligands any of  in  )W(NO)  available  NO  no a c c o u n t 1  of  1786,  undergoing d i s s o c i a t i o n  based,  display  excess  - 1  some 2 0 - 3 0 5  takes  with  cm  strong  5  latter  t h e m . The  display  2  5  also  and  ( 7 7 - C H ) W(NO) B F „ . T h i s  back-donation  between  Thus,  3  40-60 S  electron  differences  analogues.  5  amount o f  and  6  generally  ( T } - C H )W(NO) C 1 i n  anticipated  complexes  PF ~  of  [ 3 5 ] . The  6  1 7 7 0 , 1 6 9 4 and  is  various  been  are  2  inference  for  4 have  (CO) ] P F  CH C1  Such an  centre  2  2  some  by  The  )W(NO) (PPh ) ] B F „  5  in  4  yields.  substitution  salts  5  nitrosyl-stfetching 1  by  their  [( TJ -C H  5  2  good  5  BF„~ of  5  from r e a c t i o n  5  of  2  in  5  of  5  5  [ ( T ? - C H )W(NO)  [ ( T 7 - C H ) W ( N O ) {P(OPh) } ]BF 5  5  obtained  from t h o s e  spectra  IR  [(T? -C H )W(NO) L ] B F , ( 4 )  isolable  their  ligand  properties  >  are  cations  carbonyl  physical  4  2  ]  on  on  the  in  the  geometrical the  BF„~  features.  acetylenes. into  a  The  CH C1 2  2  +  34  solution of  of  (T? -C H 5  5  an e q u i l i b r i u m ,  (T? -C H )W(NO) BF„ 5  5  2  )W(NO) BF 2  results  T T  in  the  establishment  i.e.,  +  5  5  C  H  8  1  ,  4  [(T7 -C H )W(NO) (TJ -C H s  2  5  w h i c h c a n be d i s t u r b e d by t h e precipitation yield. which  The is  of  the  new  product  is  thermally  a  stable,  but  exclusively  i n an a t m o s p h e r e  hexanes  is  insoluble  or  [ (TJ -C H 5  5  5  )W(NO)  organometallic structure  2  in nonpolar but  (T^-CBH, , ) ]BF  F L  having  are the  1  (5)  )]BF ,, 1  induce in  crystalline  must  f r e e of  be  solid  solvents  such  soluble properties  "piano-stool"  and  handled  moisture  consistent  the 37%  phosphine  sparingly spectral  1  product  the  organic  1  to  2  above  completely  The  cation  Et 0  green,  unlike  discussed  benzene,  dichloromethane.  8  a d d i t i o n of  bright  derivatives  It  2  alkenedinitrosyl  phosphite  oxygen.  5  with  and as in of the  molecular  1  35  Thus an IR two  s p e c t r u m o f t h e complex as a N u j o l m u l l  strong absorptions at  the  terminal  broad,  nitrosyl  strong  tetrahedral The in CD C1 2  1  band  reaction  at  1)  5  relative  protons  2  2  respectively.  free  of t h e  free  proton  1  ) ]BF  U  at  multiplet at  5  the  5 at  I A  proton  2:1  c a n be 5  5  By  5 5.93 w h i c h  is  signals  coordinate  metals  (cf.  model  for  interpret  is  5  olefin-metal  7r-back-bonding  of to to  5  5  2.61  p r o t o n s of  C H 8  vinyl  bonding  deshielding from  W  as to  what  is  Within  Dewar-Chatt-Duncanson  [49],  it  i s tempting  indicating the  to  1 f t  transition  8  accepted  as  protons  of t h e  2  5  2/5  broad,  ( T J - C H )Cr (CO) (NO) ( T ? - C H , „ ) [ 4 8 ] ) .  of the g e n e r a l l y  this  area  between  on c o m p l e x a t i o n  ,  vinyl  the  The s h i f t  o b s e r v e d when o l e f i n s  confines  the  U  2/5 as i n t e n s e  customarily [47]  to  t o the r i n g methylene  field  to  2  5  analogy,  opposite  2  assigned  and h a s an i n t e g r a t e d  6.27.  of  ( 7 ? - C H )W(NO) B F  exactly  5  nature  resonances at 6  5 5.65 i s due  [The r e m a i n i n g  .  t o lower  5  the  a  8  equilibrium  and c o m p l e x e d c y c l o o c t e n e . ]  signals  2  5  and  U  at  are a t t r i b u t a b l e  ( T ? - C H )W(NO) B F „ 5  of  5 6 . 3 9 c a n be a s s i g n e d as t h e v i n y l 8  both  is a  2  5  cyclooctene  coordinated C H 1.41  8  signal  resonance  and  there  characteristic  - 1  intensity  The m u l t i p l e t  of  unresolved  of  cm  5. The two c y c l o p e n t a d i e n y l  5  the  Furthermore,  to  [ ( T J - C H ) W(NO) ( T J - C H , „ ) ] B F „  confirms  [ ( T ? - C H )W(NO) ( 77 - C H  that  1050  NMR s p e c t r u m of  H  6 . 3 9 and 6 . 2 7 of 5  ligands.  attributable  - 1  BF„ anion.  (Figure  2  1776 and 1674 c m  exhibits  diminished  Tj -C H 2  to  8  I A  ligand.  36  Figure  1.  [ (7} -C H 5  5  The  80-MHz  )W(NO) ( T ? - C H , ,) ]BF„ 2  5  2  8  1  in  H  NMR  CD C1 *. 2  2  spectrum  of  37  f-CM  CO  38  This  view  that  contributor  to  fact  the  that  cleaved  C H B  the  linkage  Thus,  CD C1 2  signals  which  singlet  at  [ ( 77 - C H 5  5  -W  is  bonding i s  s u p p o r t e d by  of  of  are  6.47 2  is  better  the  those  probably 3  the  free  due  to  the  a  the  readily  only  C H 8  C H 5  5  similar  than  is  6  complex,  In  being  d -acetone  to  2  principal  a-donation  due  { ( C D ) C0} ] B F „ .  the  weak,  when a s m a l l mount of  persist 5  o-bonding  relatively  capable  solution  2  )W(NO)  5  1 4  the m e t a l - o l e f i n  by L e w i s b a s e s  cyclooctene. to  the  added 1  H NMR  and  a  protons  of  1 4  manner,  the  conversion  [ (T} -C H )W(NO) (T} -C H 5  2  5  5  2  8  1 U  ) ]BF  + P(OPh)  4  ->  3  [ (7? -C H )W(NO) {P(OPh) }]BF 5  affords  the  In  familiar  view  stability  of  of  5  2  5  phosphite  the  3  complex  various  in  factors  good which  transition-metal-alkene  complexes  originally  anticipated  would  synthesize  more  complexes olefins  by  simply  such  as  Unfortunately, though the a  is  CH C1 2  not  the  2  it 5  5  replacing  has  solutions  colouration  C H 8  1 4  propene, not of  proven ( 77 - C H  when  d e c o m p o s i t i o n of  significantly  5  5  5  in  (6)  influence  the  [50],  was  it  possible  (rj -olef in) 2  to ]BF  4  5 with  " cis-2-butene  etc.  be t h e  )W(NO) B F  treated the  1 4  reaction  to 5  2  8  yield.  be  [ ( T J - C H )W(NO)  ethene,  such  blue-green  substrates,  stable  that  +C H  a  2  4  case. do  with  organometallic  diminished. Consequently,  Even  develop olefinic reactant  attention  was  39  turned  to  ascertaining  the  eventual  f a t e of  the  organic  substrates. Some o l e f i n s ,  such as a l l y l b e n z e n e ,  with  ( T ? - C H )W(NO) B F  the  final  5  5  5  2  reaction  interesting  initiation  formation the  of  positive  susceptible olef in,  and can be r e c o v e r e d  mixture.  transformations.  undergoes a clean  The  4  (but  s t e p of  Others,  For  this  to n u c l e o p h i l i c  probably then  carbon thereby by  do u n d e r g o  1,1-diphenylethene  complex w h i c h  attack  from  "dimerization",i.e.,  conversion  on an a l k e n e  react  unchanged  however,  example,  not e f f i c i e n t )  a tungsten-alkene charge  s i m p l y do n o t  another  involves localizes  rendering molecule  it of  i.e.,  (8)  ON  S  0  A  Ph  pu  Ni  N 0  CH, CPh.  40  2,3-Dimethyl-1-butene,  on t h e  double-bond  isomerization,  a  again  fact  that  (T? -C H  )W(KO)  5  5  this  the 5  2  - C  5  H  sense,  to  Thomas  it  evidence  generate  for  [ W ( N O )  be d e r i v e d )  has  [ 3 3 ] during  oligomerization  ( C H  2  C N ) , ]  3  recently  catalysis  and  rapid  2  ability  of  carbocations.  the  * may be c o n s i d e r e d , a t  2  the  incipient  c a n be n o t e d t h a t  related  )W(NO)  5  to  hand, undergoes a  i.e.,  provides  BF«  connection,  of ( 7 ?  5  other  In  electrophilicity (from  +  least  in  which a  formal  been e x p l o i t e d by Sen  of  similar  rearrangement  and  polymerization,  reactions  of  various  olef ins. It (TJ -C H  thus  5  5  5  )W(NO)  appears 2  BF  simultaneously capable donor (2)  of  that  via  f t  in  order  reaction  satisfy  f u n c t i o n i n g as  a  must  not  readily  to  cyclooctene.  described  [  (T? -C H 5  5  olefin-containing In  light  of  olefin  the  E  (T? -C H  its  5  5  5  strong  has met  „ ) ]PF  class  )W(NO)  2  must must  be  o-electron and  electrophile-induced  that  1  with  effects),  these  criteria  the  recently  Interestingly,  )CO(NO) (rj -C H  complex i n  ( 1 ) it  and e l e c t r o n i c  2  5  olefin  namely  undergo  The o n l y  is  an  reasonably  transformations. date  f o r m an a d d u c t  5,  two c r i t e r i a ,  ( c o n s i d e r i n g both s t e r i c it  to  6  of  is  also  only  compoundsf51].  BF -induced f t  the  reactions  of  41  alkenes  and t h e  fact  that  alkynes  with  transition  metal  ready  reaction  ( T? -C H  be e x p e c t e d . a  CH C1 2  2  of  complexes than  5  5  Indeed,  usually  5  solution  of  more  do a l k e n e s  readily  [52],  with acetylenes  )W(NO) B F „ 2  introduction  react  of  (7} -C H )W(NO) B F S  S  phenylacetylene  5  2  results  the  is  into  A  in  to  rapid  polymerization,i.e.,  (TJ -C H )W(NO) 5  5  5  2  PhCCH  BF  >  A  (-PhCCH-). (10)  The s o l u b i l i t y 1  H  NMR  [34].  obtained However,  reactivity  of  electrophiles.  polymer  this  this PhCCH i n  that i.e.,  polymer  from o t h e r  When  in benzene, combined w i t h  suggest  stereoisomer,  surprisingly,  that  the  spectrum  trans-cisoidal  Not  of  is  the  is  the  [34]  of  cationic  the  presence  phenylethyne  same  initiators  polymerization the  polymer  its  geometry s u c h as  contrasts of  other is  with  as  TiCl  4  the  organometallic reacted  with  42  [ (TJ -C H 5  5  [53],  )MO(CO)  (PPh ) ]BF«  2  a  3  stable  complex  is  isolated  i.e.,  [ (7? -C H 5  5  5  5  )Mo(CO) ( P P h ) ] B F „ 2  the  [ (TJ -C H 5  5  5  inefficiently  5  5  5  2  > CO 3  substrate  )Fe (CO)  d  [ ( T 7 - C H )Mo(CO) ( P P h ) (PhCCH) ] B F « .  +  When  + PhCCH -  3  (C„H  8  is  ) ]BF„,  produced  [54],  reacted  (11)  with  2-phenylnaphthalene  is'  i.e.,  (12)  As  with  the  polymerization where  the  yielding  reaction  of  PhCCH  probably  of  positive  charge  a metallovinyl  is  cation,  1,1-diphenylethene, proceeds  localized i.e.  via on  the  a  complex  the  ligand  43  If  such a s p e c i e s  with case  other as  yield  s h o u l d be p o s s i b l e t o t r a p  n u c l e o p h i l e s such as a l k e n e s .  (TJ -C H 5  5  reaction  i s formed i t  5  )W(NO) B F „  between  2  catalyzes  a  This  i s indeed the  rapid  cycloaddition  phenylethyne and 2,3-dimethyl-2-buten'e t o  3,3,4,4-tetramethyl-1-phenylcyclobutene  ,  Ph I  \/  it  i.e.,  Ph  C  C  +  II  c  III  c  (13)  A  H  H This product  ( F i g u r e 2) c o u l d  intermediate  metallovinyl  easily  be  obtained  via  an  cation, e.g.,  [w]  / ~A P h C  v  , P h  -[w]  +  A  [W] = (77 -C H )W(N0) 8  9  Thus, grounds  a  reaction  which  is  S  S  f o r b i d d e n on o r b i t a l  [ 5 5 ] i s a l l o w e d t o p r o c e e d v i a an i o n i c  symmetry  intermediate  44  Figure  2.  The  80-MHz  1  H  3,3,4,4-tetramethyl-l-phenylcyclobutene  NMR in  spectrum CDC1 . 3  of  45  co  O  CM  CO  10  CD  CO  46  56,  57].  There reactions  are  several  related  investigated  the  to  examples  equation  the  Snider  12.  aluminum h a l i d e esters  in  catalyzed  has  reactions  between  methyl  p r o p y n o a t e and  1 . 2 - d i s u b s t i t u t e d ethenes  stereospecific  cycloaddition,  e.g.,  2  + However,  reactions give  C0 Me  \  /  2  (14)  1,1-disubstituted,  tetrasubstituted  the  between  and a l k y n o i c  co Me  example,  of  thoroughly  alkenes  [58],  For  literature  ethenes  give  trisubstituted  exclusively  and  ene a d d u c t s ,  e.g.,  COjMe  > The  (T} -C H 5  5  5  + )Fe(CO)  cyclobutenes [59].  However,  structure  of  and  (15)  cation  dienes  the the  tetrasubstituted  2  CO-Me  also  from a l k e n e s  reaction olefinic  alkenes  catalyzes  is  yield  only  formation  and p r o p y n o i c  strongly  reactant;  the  dependent  esters on  1,1-disubstituted  lactones.  of  the and  47  R  A vinyl  8SB—COOMe  cation  +  is  X  (16)  presumably  formed  1-bromo-1-(4-methoxyphenyl)propene p r e s e n c e of  AgBF„  [60],  in with  the  reaction  2-butene  of  in  the-  i.e.,  (17)  Finally, alkenes  C H A1C1 2  with  5  2  catalyzes  1-alkynes  the  [61],  [2+2]  cycloaddition  of  e.g., CH  (18)  H  It  was  found t h a t d i a l k y l s u b s t i t u t e d  p r o d u c t s or  trimerize  In  give  polymeric  to hexaalkylbenzenes. T r i m e r i z a t i o n  1,3,5,-trialkylbenzenes 1-alkynes.  alkynes  also  o c c u r s as a s i d e  addition,  further  reaction  reaction  leads  to  with to  bicyclo[2.2.0]hexenes. Similar  behaviour  to  this  latter  reaction  is  observed  48  in  the  ( T J - C H )W(NO) B F S  allowed  5  obtained.  the  2  t o warm t o  products other are  system.  5  'H  NMR  observed at  4  If  the  room t e m p e r a t u r e  than Several  new m e t h y l  spectrum. m/z v a l u e s  In  the  mass  indicative  of  the  ( T J - C H )W(NO) B F  quenched  by  the  addition  mixture  to  the  of  activity  initial  5  5  Indeed,  reveals  for  that  2  of  is  30 m i n ,  product.  the  only  peaks of  catalyst  a  the  in are  another  Conversely,  acetonitrile.  infrared  observed  spectrum,  and p r e v e n t s an  are  addition  5  the metal  phenylethyne.  and s t i r r e d  resonances  unit  to  mixture  1-phenyl-3,3,4,4,-tetramethylcyclobutene  phenylethyne  coordinates  reaction  all  system  This  is  presumably  coordination  spectrum of  the  nitrosyl-containing  of  reaction  species  is  [ ( T ? - C H )W(NO) (CH CN) ] B F „ . 5  5  5  2  Attempts cycloaddition rewarding.  3  to generalize reactions  When  to  acetylenedicarboxylate,  the  intermediate  or  reaction  proceeds  indicates  that the  promoting the  5  5  2  substrates  is  replaced  methyl  reaction  have by  to  be  less  readily  steric methyl  not  no  12  [2+2] may  The  dimethyl  cycloadducts  be  Restrictions severe.  unique stability  on t h e fact  groups  nucleophi1icity  are  not  probably of  the  overly aid  the  alkene.  to of  alkene  that  with a t e t r a s u b s t i t u t e d  constraints  been  phenylpropyne,  proynoate,  1-hexyne,  carbocation.  appear  fact,  5  T h i s c o u l d be r a t i o n a l i z e d by t h e  substrate  In  lane,  formed. U n f o r t u n a t e l y ,  phenylethyne.  ( T J - C H )w(NO) B F „ - c a t a l y z e d  other  phenylethyne  trimethyl(phenylethynyl)si  are  the  the  reactant  demanding. reaction  by  Cyclohexene  49  also  reacts  with  ( T J - C H )W(NO) B F 5  S  5  2  readily.  T T  Under  reaction  .  phenylethyne However,  the  same  o c c u r s . However,  temperature  for  A lack  of v i n y l  spectrum  suggests  that  the  reaction  conditions  as  time,  all  of  expected b i c y c l o [ 4 . 2 . 0 ] o c t e n e ,  proceeds  is  of less  12, no  warmed t o  room  the phenylethyne  proton resonances the  presence  equation  when t h e m i x t u r e  a p e r i o d of  consumed.  the  in  isolated  in  the  product  is  is  'H  NMR  not  the  i.e.,  Ph (19)  In  addition,  double that  that  t h e mass s p e c t r u m shows t h a t which  reaction  addition  is  19  reaction  expected. does  that  take  the p a r e n t  These  observations  place  but  c o u p l e s two of  is  mass  is  suggest  f o l l o w e d by an  the p r o d u c t m o l e c u l e s .  (20) Ph  (d) is  Reactions  attempted  with anionic  with  the  silver  s u c h as p - t o l u e n e s u l f o n a t e , to  the  tungsten centre,  nucleophiles. salt  of  reaction  1  a c o o r d i n a t i n g anion  t h e a n i o n becomes  i.e.,  If  firmly  bound  50  (rj -C H 5  5  5  )W(NO) C 1 + A g O S 0 C H C H 2  2  (T} -C H 5  5  (This  organometallic  treatment of  of  5  6  4  )W(NO) O S 0 C H C H 2  5  5  by  ( 7 } - C H )W(NO) B F 5  5  various  2  anions.  successfully,  5  However, it  [25].)  This  centre  is  in order  (21)  amount  binding  suggests  to e x p l o i t  mandatory  in CH C1 2  2  so  that  that  electrophile thus  which e i t h e r  react  to permit  Fortunately,  acid  metal  limitation  solubility  + AgCl(s).  3  rapid  [PPN]  integrity  is  maintained.  with CH C1 2  salts  +  2  with  are  reactions  the  the  not  use  the This  anionic  insufficient  (7? -C H 5  of  of  or have  by  reactivity  the d e s i r e d  excludes  reaction  this  of that  would be p r o n e t o n u c l e o p h i l i c a t t a c k  nitrosyl-containing  reagents  4  2  the  4  proceed promptly  practical  6  ( T 7 - C H )W(NO) H w i t h a s t o i c h i o m e t r i c  anion 5  2  p r o d u c t h a s been o b t a i n e d p r e v i o u s l y by  anhydrous p - t o l u e n e s u l f o n i c  the  ->  3  5  5  )W(NO) B F 2  4  .  hampered  by  either  type  chemistry,  restriction. As (T? -C H  an u n r e m a r k a b l e  5  5  5  )W(NO) B F 2  well-known  (rj -C H 5  5  5  example o f t h i s  reacts  4  cleanly  ( 7 ? - C H )W(NO) B r 5  5  )W(NO) B F « 2  5  2  +  with  complex,  [PPN]Br  of  [PPN]Br  to y i e l d  i.e.,  ->  (77 -C H ) W (NO) Br 5  5  5  2  [PPN]BF .  significantly,  treatment  of  ( T? -C H 5  5  5  )W(NO) B F 2  + (22)  4  More  the  4  with  51  [PPN]BH„  produces the c o r r e s p o n d i n g metal  ( T 7 - C H )W(NO) B F 5  5  2  5  + [PPN]BH«  f t  >  hydride,  [PPN]BF,  i.e.,  +  "BH "  (TJ -C H )W(NO) H,  (23)  5  5  The  isolated  (56%)  yield  of  5  compares f a v o u r a b l y  the  reaction 5  5  the  yields  with  (r? -C H  23%  respectively)  5  cleanest  5  obtained 5  2  5  )W(NO) H f r o m t h i s  5  reaction  2  previously  reported  from  Na[A1H (OCH CH OCH ) ] 2  (i.e.  2  5  with that  of  ( T 7 - C H )W(NO) C 1 5  ( 7j -C H  61%)  and i s  from  )W(NO) C 1 or  5  In  5  fact,  and most c o n v e n i e n t  2  3  considerably  reactions  [ (rj -C H  2  [25].  the  2  of  NaBH„  2  reaction  method f o r  with  2  better  )W(NO) (CO) ] P F  5  6  +  3  than  (in  THF)  (13%  and  23 r e p r e s e n t s  the  synthesis  the  of  the  h y d r i d o n i t r o s y 1 complex. The  affinity  demonstrated reaction  by  of  reaction  5 _  C H 5  22  5  ) W ( NO) BF 2  is  5  2  5  +  for  a  also  with bromotriphenylmethane,  ( T ? - C H )W(NO) B F „ 5  (rj  Ph CBr  evident  ion  during  its  )W(NO) B r  +  i.e.,  >  3  halide  ( 77 - C H 5  5  5  2  [Ph C]BF„.  (24)  3  Hence,  as  more p o t e n t the  far  halide  Br"  electrophile  nucleophile  [28].  as  This ions  involved,  pronounced may  is  concerned,  than P h C . 3  the  reverse  affinity  account  +  of for  ( 7 ? - C H )w(NO) 5  In of  5  5  contrast, reaction  2  is  +  when H" 24  5  the  2  5  fact  is  occurs  ( T ? - C H )W(NO) B F 5  a  a  for that  52  [ {(T7 -C H 5  5  5  )W(NO) } C 1 ]BF 2  intermediate Of  the  is  ft  not  d u r i n g the p r o g r e s s of  greater  leading  2  interest  than  possibility  5  that  type  ( 7 ? - C H )W(NO) R  directed  5  established (1)  the  (R. = a l k y l  or a r y l ) .  synthesis  metathesis  even 5  of  between  5  2  detectable  Evidently  this  arylating  g r o u p s as w e l l the  compounds  displace  gentler  are agents  5  studies  5  2  to  yield  quantities  is  Cl~  When  of the  Previous  fail  to  (2)  utilized  derivatives  5  reagents  functional  be  ( 7 ? - C H )W(NO) C 1  o r g a n o l i t h i u m and G r i g n a r d selectively  compounds was  c o m p l e x e s [22]  R L i a n d RMgX r e a g e n t s  spectroscopically 5  these  because  of the  are too potent  and  attack  other  [62].  and  more  selective  R A1 3  employed  as  the  alkylating  in place  of  RLi  or  RMgX,  or the  transformations  ( 77 - C H 5  5  5  )W(NO) C 1 . 2  + R A1 '  > (T? -C H 5  3  5  5  )W(NO) R 2  + C1A1R  are  s u c c e s s f u l when R = C H  for  the congeneric  3  o r P h . However,  C r and Mo  an  routes  features:  reactions  ( T 7 - C H )W(NO) R .  synthetic  might  2  or a r y l  the f o l l o w i n g  and v a r i o u s  5  o f new a l k y l  2  at  5  as  1.  (X = H o r B r )  2  5  the p r e p a r a t i o n 5  5  new  ( 7 ? - C H )W(NO) B F „  for  5  reaction  these  t o t h e ( 7 ? - C H )W(NO) X 5  detectable  complexes,  2  (25)  unlike reaction  have  53  25  is  of  not g e n e r a l l y  a variety  fact  is  of  electrophilic carbon  5  5  a  the  2  reflection  2  5  to cleave and  the  bond  This  greater in  the  [26,63].  5  bonds  of  metal-chlorine  ( 7 ? - C H )W(NO) B F „ 5  synthesis  complexes.  5  reactant  Fortunately,  for.the  ( T ? - C H )W(NO) R  probably  strength tungsten  of  applicable  a  so  is  indeed  of  main-group-metal  variety  produce  the  sufficiently  desired alkyl  to  and a r y l  derivatives. In an  a manner a n a l o g o u s  equimolar  (T? -C H 5  5  5  amount  )W(NO) B F „  results  2  g r o u p from B t o W,  (T7 -C H 5  5  5  of  )W(NO) B F « 2  to reaction Na[BPh ]  25, the  to a CH C1  u  2  in a clean  transfer  relatively  complex  +-Na[BPh,]  > (T7 -C H  mode  from t h i s  conversion  reaction  of  probably  involves  ( 7 } - C H )W(NO) 5  5  5  5  success of  BPh  3  of  reactivity  5  )W(NO) C 1  initial  aromatic as d e p i c t e d  of t h i s since,  5  yield  i s comparable  (rj -C H  2  phenyl  )W(NO). Ph  5  [ 6 4 ] . The 48% i s o l a t e d  electrophilic  a  i.e.,  rare  5  of  s o l u t i o n of  2  of  2  5  + NaBF  a  addition  2  (r? -C H 5  to that  and P h A l  anion  transformation  refects  as noted above,  (r? -C H 5  5  5  5  (26)  )W(NO) P h 2  from the  [22]. Reaction  substitution Scheme  5  obtained  exchange  in  3  f o r an o r g a n o b o r o n  of  3  + BPh ,  4  followed of  I.  BPh  3  Certainly,  the m e d i a t i n g )W(NO) P h 2  26 by by the  effect  cannot  be  Scheme T  WBF + Na[BPh ] • 4  4  C H 2 C l g  »  W ©  W-Ph + BPh,  W  B P h + NaBF 3  0  4  4  BPh, ©  3  where W = (77 -<^H )W(NO). 5  5  cn it*  55  prepared  using n u c l e o p h i l i c  Furthermore,  the f a c t  demonstates  that  innocent  that  [BPh ]"  electrophilic The prepared  during  organometallic  phenyl  derivative  i n moderate  (T7 -C H 5  5  5  yield  )W(NO) B F „  sources  reaction  26  may  4  counterion  carbanion  not  the  PhLi.  occur  also  function  a s an  does  always  attempted  isolation  of  cations. of  ( T 7 - C H )W(NO) 5  5  5  c a n a l s o be  2  by e m p l o y i n g P h „ S n ,  + Ph„Sn  2  such as  i.e.,  > ( 7 ? - C H )W(NO) P h 5  5  5  2  (27)  + Ph SnBF . 3  This  transformation  indicates  that  complexes of  is  very  this  method  is general,  limited  the main-group-metal  is  the  fact  affords  that  5  of only  reagent.  the  5  2  to  reaction  forming  5  5  by t h e r e a d y  analogous  use  26  (r? -C H  Consistent  t h e new b e n z y l d e r i v a t i v e ,  ( T 7 - C H )W(NO) B F „ 5  similar  5  )W(NO) R 2  this  view  (PhCH )„Sn 2  + (PhCH )„Sn  > (T? -C H 5  2  5  5  2  lower  than  that  of t h i s  stable  of t h e p h e n y l  [65]  i.e.,  )W(NO) C H P h 2  + (PhCH ) SnBF„,  a l t h o u g h the y i e l d  and  availability  with  of  a  olive-green  3  solid  complex o b t a i n e d  from  2  (28)  (18%)  is  reaction  27 . As d i s c u s s e d e a r l i e r , ( T 7 - C H )W(NO) C 1 . 5  5  5  2  (C H ) A1  However,  2  5  3  it  does reacts  not  react  readily  with with  56  (T7 -C H )W(NO)2BF4  at  (T? -C H )W(NO) BF  + (C H ) A1  5  5  5  5  5  2  5  4  i.e.,  -78°,  2  5  >  3  ( T? -C H  )W(NO) C H  5  5  5  2  2  5  + { ( C H ) A 1 B F } , (29) 2  the  new t u n g s t e n - e t h y l  from  the  final  complex b e i n g  reaction  mixture.  has n o t been a s c e r t a i n e d . ] because  both  of  the  ( i 7 - C H )W(NO) R (R 5  5  5  2  =  physical  properties  analogue.  These green  solvents for  (including  short  that  or  5  of  decomposition.  Without doubt,  complexes  other  to the IR  their  by  inherent  unsuitability spectra  5  two  nitrosyl  ligands.  decrease  in  reflects  the  withdraw  Ill)  strong  5  electron  density  The r e l a t e d  noticeable  of  be a t t r i b u t e d  in to  these  CH C1 2  absorptions  2  these  from t h e c e n t r a l  2  5  which  5  ligands  to  metal.  o f (rj -C Me ) W ( N O ) BF . 5  5  2  terminal  H > CH Ph > C H of  these  m e t h o d o l o g y . The  assignable  ability  chemistry  organic  prepare  2  t h e o r d e r X = C l > Ph diminishing  in  )W(NO) X c o m p l e x e s  frequencies  exhibit  must be a s c r i b e d t o  synthetic  absorptions  The  to  cannot  but rather  5  The new  of the methyl  undergoing  routes  of the p r e v i o u s  remarkable  may be e x p o s e d t o a i r  the f a i l u r e  instability  is  soluble  without  preparative  of a l l the ( T ? - C H  display  very  yield  o f t h e aluminum  t o those  and they  time  16%  complexes  2  solids are  4  Lewis a c i d s .  CH Ph)  are similar  hexanes),  periods  are  2  in  conversion  reactants 2  isolable  [The f a t e  This  C H  5  2  M  It  is  57  possible  to  extend t h i s  chemistry  pentamethylcyclopentadienyl discussed  in  the  analogues  previous  complexes r e q u i r e d  for this  prepared  by  procedures  [32, 25],  5  portion  straightforward  5  of  sections.  the  complexes  The  new  the  study  of  extensions  precursor can  of  be  standard  i.e.,  ( 77 - C M e )W(CO) N 0 + ClNO 5  t o encompass some o f t h e  > ( T J - C M e )W(NO) C 1 5  2  5  5  2  + 2 CO (30) and ( 7 ? - C M e )W(NO) C 1 + Na [ A 1 H ( O C H C H O C H ) 5  5  5  2  2  2  2  3  2  ]  > (rj -C Me )W(NO) H 5  and t h e i r  physical  analogues.  Interestingly,  ( 77 - C M e )W(NO) B F 5  5  properties  5  2  two c o m p o u n d s ,  a  5  5  those  CH C1 2  c a n be g e n e r a t e d  (31),  2  of  the  C H 5  solutions  2  from  either  of  of  these  5  2  > (rj -C Me 5  4  5  5  )W(NO) B F „ 2  + AgCl  ( 7 ? - C M e )W(NO) H + P h C B F „ 5  5  5  2  > ( TJ -C Me ) W(NO) B F 5  3  5  5  2  3  32  i s , of c o u r s e ,  1, b u t r e a c t i o n  33 h a s no  the d i r e c t  precedent  in  analogue the  of  C H 5  5  (32)  4  + PhC H.  Reaction  5  i.e.,  ( 7 ? - C M e )W(NO) C 1 + A g B F 5  resemble  5  (33)  reaction system.  58  [Indeed, CH C1 2  treatment results  2  [ ( T? -C H 5  5  5  2  3  (rj -C Me 5  at  4  2  a  in t h i s  )W(NO) B F  5  2  than  analogue. C Me 5  This  ligand  5  ligand.  5  which  u  2  which  - 1  those  is  a  better  Consequently,  it  5  readily  (7? -C Me  )W(NO) B F 2  5  5  + PPh  a  its  5  donor  lower  - 1  fact  in  that  than  the  the C H 5  anticipated  a  )W(NO) B F « .  somewhat  weaker  Nevertheless,  2  it  i.e.,  >  3  5  product  hand,  the  being 5%  5  5  5  2  2  ( 77 - C M e )W(NO) B F „ 5  5  5  2  5  obtainable yield  ( 77 - C M e )W(NO) C H  5  of  from t h e  in the  5  5  2  3  63% y i e l d . new  On t h e  ethyl  3  > ( 7 j - C M e )W(NO) C H 5  5  2  even  less  r e a c t i o n 29.  appealing  than  other  complex,  5  + {(C H ) A1BF,,}  is  (34)  f t  conversion  + (C H ) A1 * 2  5  that  [ ( 77 - C M e ) W ( N O J ( P P h ) ] B F ,  the  of  cyclopentadienyl  electron  be  reaction  absorptions  cm  the  3  5  20-30  of  spectrum  nitrosyl  by  well  ( 77 - C H  IR  reflects  forms a d d u c t s w i t h P P h ,  5  5  than  displays  c a n be r e a s o n a b l y  2  electrophile  The  a r e some  simply  in  3  immune t o f u r t h e r  exhibited  feature  Ph CBF„  precipitation  is  2  with  2  [28].)  in CH C1  t t  5  the  ( 7 7 - C M e 5 ) W(NO) B F m a y 5  5  solvent  1730 and 1645 c m  energy  ( ? 7 - C H )W(NO) H in  ) W (NO) H ] B F  with Ph CBF 5  of  that  o f its C H 5  5  5  2  analogue  2  2  5  (35)  from  59  The c h e m i s t r y  IV)  compouds  from  5  5  ( 7 j - C H ) W ( N O ) X by 5  5  new  5  a  by A g ( l )  derivatives  previously w i t h AgBFj,  5  trihapto  salts  prepared  this 5  in a c e t o n i t r i l e  3  5  3  5  5  3  5  + AgBF 5  ligand  via  an  in this  by h a l i d e  [ (r? -C H 5  5  3  route the  -> A g l  )W(NO) ( T J - C H ) (CH CN) ]BF« . 3  5  ion  [ 4 0 ] reacts  5  3  stable,  analogous r e a c t i o n  5  3  yellow  [66].  salt  The  (36)  has been  acetonitrile  easily  replaced  i.e.,  ) W ( N O ) ( T ? - C H ) (CH CN) ] B F „ + KX  >  3  5  linear  synthetic  new t u n g s t e n c o m p l e x can be  ions,  a  i.e.,  ft  molybdenum c o n g e n e r o f t h i s  obtained  formally  of c o m p o u n d s . T h u s ,  solution,  + [ (r? -C H  The  of  The  ligand. Halide  a useful  class  are  ( T) -C H )W(NO) ( 7 j - C H ) I  )W(NO) ( T ? - C H )I  5  allyl  is also  in  complexes.  replacement  2  by  allyl  (X = h a l i d e )  5  3  ligand  abstraction  ( 77 - C H  related 3  5  nitrosyl  5  some  ( 7 ? - C H ) W ( N O ) ( T J - C H )X  derived  to  of  3  3  5  KBF„  + ( T 7 - C H )W(NO) ( T J - C H )X ( 3 7 ) 5  3  5  5  5  3  X = C 1 o r Br  The  'H  that  their  NMR  spectra  allyl  of these  three  ligands display  the  crystallographically 3  5  specrum  5  3  of  same  a, ir-  indicate  distortion  verified  (TJ -C H )W(NO) (TJ -C H )I [40] . 5  new c o m p l e x e s  5  For  example,  (T? -C H )W(NO) (T? -C H ) C 1 5  3  5  5  3  5  for the  clearly  1  H  shows  NMR the  60  inequivalence  of  the a l l y l  protons  (see  Figure  3).  Figure  3.  The  80  ( 7 ? - C H )W(NO) ( V - C H ) C 1 5  5  5  3  5  MHz in  1  H  CDCI3*.  NMR  spectrum  62  63  CHAPTER  THE  EFFECT OF. NITROSYL LIGANDS ON METAL-CARBON.a  The work answer  of  described  some  and a l k y n e s This  THREE  questions bonded t o  chapter  alkyl  ligands 5  (M  One c-bonds  2  previous  regarding  the  in  5  influence  the  5  5  attempts  Cr,  reactivity  of  of  the  common  is  metal-alkyl  cleavage  to  or  2  study  metal-alkyl  the  to  alkenes group.  reactivity  i.e.,  can  functional  the  groups  bonds?  reactions  fall  of  functional  +  W)  by e l e c t r o p h i l e s .  bonds g e n e r a l l y  attempted  reactivity  systems,  Mo  the  most  the  5  congeneric =  chapter  ( i ? - C H )W(NO)  summarizes t h e  ( T } - C H )M(NO) 5  in  BONDS  of  metal-carbon  Cleavage  reactions  into  two  classes  it  intriguing  of  [52],  insertion-like, M-R and  + E  > M-E-R  eliminative, M-R  + E  With regard  > RE + M. to  the  transmetallation  (T} -C H 5  5  5  )M(LO) C H 2  second p r o c e s s ,  is  that  the  reaction  3  + HgCl  2  > CH HgCl 3  +  (V-C H 5  5  )M(LO) C 1 2  (38)  64  p r o c e e d s much more r e a d i l y =  Fe  and  L = C [67].  charge arguments. and  the  complex  of  this  been  the  caveat  of  the  reactions  Experimental Reaction  of  (T? -C H 5  5  mmol)  mmol).  in  the  orange  time,  the  reaction  CH C1 , 2  of  a 3 x 6  developed Addition  of  3  THF  time  2  of  was a  5  Fe(ll),  nitrosyl  to e l e c t r o p h i l i c  attack.  further  investigation  Therefore,  as m e r c u r i c  a study  has  complexes  chloride,  as aluminum  into  tri-  trichloride.  [68].  )Mo(CO) C H 3  at  2  [68]  5  taken  solid  to  a small was  to  The o r a n g e  the  end of  dryness (ca.  in  5 mL)  Elution that  eluate, led  (0.35  2  the  for  precipitated  transferred  fraction  (0.35  room t e m p e r a t u r e  s o l u t i o n . At  Florisil.  the  2  was added s o l i d H g C l  extract  of  to  5  stirred  was  bright-orange  3  5  HgCl  tan-coloured  mixture  hexanes  with  5  5  supernatant  column  ( i 7 - C H )Mo(CO) C 1 5  the  ( 77 - C H  reduced-pressure concentration 5  Cr(0)  some a l k y l n i t r o s y l  (25 mL)  resulting  cm a  )Mo(CO) C H  was e x t r a c t e d  and the  2  5  The m i x t u r e  from  residue  complex c o n t a i n s  One,  i o n s as w e l l  solution  h d u r i n g which  The  formal  Section  To a y e l l o w 1.3  of  electrophiles  and d i p h e n y l c a r b e n i u m  4.5  in Chapter  when M  by  contains  phenomenom seemed w a r r a n t e d .  made  g,1.3  nitrosyl  complex  w i t h such t y p i c a l  g,  the  been r a t i o n a l i z e d  s h o u l d be more s u s c e p t i b l e  Mindful of  T h i s has  Since  carbonyl  when M = Cr and L = N t h a n  followed  vacuo.  amount to  with  was  that  the  of top  CH C1 2  2  collected. by  slow  crystallization  of  s o l i d was c o l l e c t e d  by  65  filtration  in  Anal.  28% y i e l d  Calcd for  17.11.  F o u n d : C,  2050,  1971 c m " . specrum  8  226  +  5  C,  3  H,  'H NMR  (probe  ([P-CO] ),  g).  C H 0 ClMo:  34.00;  1  mass  (0.10  1.72;  0,  (CDC1 ):  17.16.  5 5.65  3  no  34.25;  heating):  2  (s).  0, v(CO)  2  Low-resolution  282  198  +  1.80;  IR(CH C1 ):  m/z  ([P-2CO] ),  H,  (P ),  254  +  ([P-3CO] ),  163  +  ([P-3CO-C1] ). +  Reaction  of  ( T ? - C H )MO (NO) C H 5  A green 2.0 g,  mmol) 2.2  the  i n THF  mmol).  The  wide  solvent  residue  band  under  (T^-C H 5  5  IR(CH C1 ): 2  6.09  (s,  Reaction  5  of  Solid  which  5  [32]  1.13  was  3  6  (0.78  in  was  4 mL  (0.57  2  room  removed  benzene  t o p of  collected.  in and  a 2 x 15 developed  Removal  of  the  followed  identified  as  a  by left  mixture  a of  CH HgCl. 3  1759 ( s ) ,  1666 (vs)  cm" . 1  'H NMR:  6  CH ). 3  5  Ph CPF  solvent  g,  at  dichloromethane/hexanes  and  5  stirred  pressure,  was  (s,  (0.47  with s o l i d HgCl was  the  [22]  3  w i t h benzene s l o w l y  ( T ? - C H )Cr (NO) C H 5  2  s y r i n g e d onto the  Elution  p(NO)  2  C H ),  mixture  was d i s s o l v e d  s o l i d which 2  2  before  from  )Mo(NO) C 1  HgCl  5  treated  reduced  recrystallization light-green  5  was  was  Florisil.  green  5  h  solution  3  ( T 7 - C H )Mo(NO) C H  reaction 2.5  The g r e e n  resulting  of  (25 mL)  for  cm column o f a  2  5  solution  temperature vacuo.  with  5  2  g,  3  with  2.0  Ph CPF 3  mmol)  6  was  added  to  a  66  stirred, 2.0  green  mmol).  s o l u t i o n of  The c o l o u r  golden-brown.  The m i x t u r e  1  column o f solvent 1  alumina  i n vacuo  H  was to left  Low-resolution  258  +  Reaction A (0.12  of  was  ( T? -C H  changed  5  s p e c t r u m of the  starting  at  the  was  diethyl  and  washed  in  material ca.  to  2  cm)  Removal  of  Ph CCH . 3  15H, C H ) , 6  (probe  1840  ( 3 x 3  filtrate.  to  displayed  1740 and c a .  of  g,  changed  solution  ca.  CH C1 2  Ph CPF 3  of  5  no  3  2.19  (s,  3H,  heating):  (0.20  6  with  the  revealed  and t h e and  bright  a green  At  for  through mL)  was  5  m/z  6  5  was  2  treated  The r e a c t i o n  ca.  1 h and  end  of  complete of  The  an  1680 c m ' . A d d i t i o n o f 1  the  solution  cloudy  medium-porosity added  to  the  s o l i d w h i c h was c o l l e c t e d ether.  time,  consumption  The somewhat a  colour  a new s p e c i e s  of  solid  was  IR of  with PPh  3  to  reaction frit  filtrate by  an  mixture  its  that  [22]  3  with  g).  colour  green.  3  5  presence ca.  PhC PF  ( T 7 - C H ) M O (NO) C H  (7 mL)  2  caused the  (30  with  3  solution  1770  filtered  ether  precipitate  )MO(NO) CH  solution  0.50 mmol)  mixture  (0.34  +  olive-green.  (0.13  back  (m,  room t e m p e r a t u r e  at  change  5  of  y(NO)'s g,  8 7.3-7.1  green  amount  to  the  through a short  mass s p e c t r u m  5  stirred  at  immediately  0.16 g (31% y i e l d )  3  0.50 mmol)  equimolar  spectrum of  [22]  3  [(P-CH ) ].  bright g,  2  leave a c o l o u r l e s s  3  243  5  solution  filtered  NMR ( C D C 1 ) :  (P ),  5  absorptions  CH ). 3  5  the  An i n f r a r e d  nitrosyl-stretching cm" .  of  ( rj -C H ) Cr (NO) C H  and to  filtration  identified  as  the  67  dichloromethane (0.21  g,  cm" . 1  (d,  66% y i e l d ) .  H  1  solvate  5H,  NMR  [IR  J=1.2  colourless  2  solution  which,  s o l i d which  yield)  by  its  was  2  5.62  (m,  (s,  (s),  taken  when e v a p o r a t e d  characteristic  as  1710 6  (vs)  2  to  to  Ph CCH 3  physical  The  2  dryness. to  The  yield  dryness, (0.09  3  6.40  5  CH C1 )]  petroleum ether  identified  [35]  6  15H, C H ) ,  0.6H,  was  light  3  1792  i^(NO)  2  filtrate  into  )MO(NO) (PPh ) ]PF  6 7.7-7.5  Hz),  extracted  a white  5  5  6  5  was  5  (CH C1 ):  slightly-green-coloured residue  [ (T? -C H  (d -acetone):  C H , 5  of  gave  g,  properties  a  67% (vide  supra).  Reaction To CH C1 2  mmol)  5  5  (25  2  was  of  the  ZnCl  an  2  (0.136  2  5  5  mL,  5  At  0.21  the  a was  a  After  the  removal  5  5  involatile  the  for  2 h during  of  concentrated the  2  solvent  liquid.  (0.19 g ,  1.1  x  4  (0.14  in  from t h e  The which from  time,  the  cm column of frit.  The  to c a .  concentration  product  1.0  changed  vacuo  g,  in  mmol).  that  medium-porosity  organometallic of  3  mmol)  g,  2  ( r ? - C H )Cr (NO) C1 5  1.00  solution  end  through  on  g, 2  h e x a n e s were added and  filtration,  Ph CHCl  supernatant  filtered  until  as  with  room t e m p e r a t u r e  filtrate  precipitated.  3  3  (rj -C H ) Cr (NO) C H  (0.18  at  supported  continued  2  added  2  was  30 mL of  Ph CHCH  anhydrous  golden-brown.  golden-brown  by  2  Ph CHCl  stirred  suspension  mL,  5  was  colour  to  Florisil  of  mL)  and n e a t  the  green  ( T ? - C H )Cr (NO) C H  a slurry  mixture time  of  66% was  10 was  yield) collected  filtrate  left  68  1  H NMR (CDC1 ):  6 7 . 23 ( s ,  3  J=7.3 Hz, CH),  Reaction A  of  mmol)  (d,  2H,  s  in  of  25 mL of  Ph CPF . 3  temperature,  2  s o l u t i o n of  S  2  was  2  an IR  presence  of  spectrum  a  new  nitrosyl-stetching - 1  .  [ (T7 -C H 5  5  was  5  by 2  taken  3  to dryness  (80% y i e l d )  of  A (T7 -C H 5  5  at  [22]  5  0.72  for  starting  1.9 mmol)  5 min a t  under  and  species  hexanes  1770  (25  which  identified  75% y i e l d ) .  reduced pressure  The to  the with  ca.  solid  room  solution  and  of  g, (1.9  was a d d e d t o  and g,  g  material  1680  addition  (0.84  (0.47  olive-green  ca.  g,  7.4-7.1  (m,l5H,  5  5  2  (0.27 room  g,  2.0  3  (30  (0.37  3  g,  mmol).  temperature  C H ), 6  5  with A1C1  5  2  3  the  6  with  a light-green  ( T ? - C H )Cr (NO) C H  )Cr ( N O ) C H  s o l i d A1C1 stirred  of  dichloromethane  5  1H,  the mL) was as  filtrate  leave  0.37 g  3  3  of  2  stirred  the  (0.49  6  (q,  Ph CH.  'H NMR ( C D C 1 ) :  Reaction  2  filtration  ) M O ( N O ) P P h ]PF  3  treated  of  Subsequent  caused the p r e c i p i t a t i o n collected  Ph CPF  )MO(NO) C H  a b s o r p t i o n s at  mixture.  4.14  5  nitrosyl-containing  Triphenylphosphine  reaction  5  being  showed c o m p l e t e c o n s u m p t i o n of  cm  with  S  5  After  6  2  (T7 -C H  CH C1  6  3  5  5  C H ),  CH ).  ( T ? - C H )Mo(NO) C H  green  1.9 minol)  1.62  10H,  mmol)  The for  (s,1H,  CH).  3  mL) 2.0  5.59  solution was  reaction  of  treated  with  mixture  was  2 h d u r i n g which  time  its  69  colour  changed  light-green filtration  solid  being  Florisil.  band  pressure mL),  was  platelets  (CDC1 ): 3  of  with CH C1 2  collected  by 5  5.69  2  (s).  5  5  v{HO)  The  the  dark  t o p of  a  Addition  1816 ( s ) ,  (0.25  1711  a  removed by  in vacuo  concentrated  [32]  and  to  ca.  a 3 x 7 cm column  of  concentration 2  green  s o l i d was  developed  2  25 mL.  slow  to  concentrated  and  ( r ? - C H )Cr (NO) C 1  ( C H C 1 )' 2  was  s y r i n g e d onto  to a p p r o x i m a t e l y  followed  IR  filtrate  Elution  which  yellow-green  precipitated.  and t h e  5 mL b e f o r e of  from  golden-brown under  reduced  hexanes  afforded g,  (vs)  60%  (25  golden  yield).  cm" . 1  1  H  NMR  70  Results  and D i s c u s s i o n  Although bond  mercuric  in  halide  the  cleavage  alkyl  of  the  iron-carbon  derivatives  d i c a r b o n y l ( 77 - c y c l o p e n t a d i e n y l ) i r o n  has  [67,69],  electrophilic  5  the  reactions  same i s  of and  unreactive  [70],  "orange  HgCl  of  While  (r} -C H  has  now  is  5  5  3  been  5  5  5  5  2  with HgCl  5  )Mo(CO) C H 3  2  5  of  studied cleavage  chromium,  )Mo(CO) C H 3  reportedly  5  is  3  yields  only  upon t r e a t m e n t  found  be  HgCl (r? -C H  2  formed  )Mo(CO) C H  S  5  insoluble material"  3  5  (r? -C H  3  5  )Mo(CO) C 1 c a n e a s i l y  5  5  5  well  complexes  )Mo(CO) C H  5  It  precipitate (rj -C H  (r? -C H  for  nitrosyl  tungsten.  rather  [71].  2  true  analogous  molybdenum  an  not  been  of  that,  with  although  a  during  the  reaction,  isolated  from the  reaction  in  2  tetrahydrof uran,  i.e.,  2  >  5  ( 7 7 - C H )Mo (CO) 5  5  5  3  CI. (39)  The  relatively  lack  of  low y i e l d  reactivity  ( T J - C H )Mo(CO) R 5  5  5  related  3  substituted P(C„H ) ) [70],  3  the  rather  cleanly  Presumably,  the  than  less  5  of  a  ( 77 - C H 5  reaction,  analogue,  derivatives  complexes  react  methyl  complexes are  dicarbonyl  an e l e c t r o n i c ,  9  of  from the  w i t h HgX  iron.  )Mo(CO) 2  (X  p r e s e n c e of  as  the  suggests that  the  nucleophilic  steric, 5  as w e l l  2  T h i s appears effect  (L)CH  = CI, the  than  3  Br,  better  the to  since (L  = PPh  I donor  or  be the  3  or SCN)  ligands  71  than  CO e n h a n c e s  reactivity  towards  In  the  it  (rj -C H 5  5  HgCl .  light 5  of  )Mo(NO) R  above,  (R  2  =  CH  w i t h the  mercuric  in  the  infrared  and  1640 c m  - 1  salt,  the  in  and a r e  replaced  by a new  1665  cm  the  - 1  ,  ( T ) - C H )Mo(NO) C 1 . 5  5  which  2  shows t h a t  organometallic  2  react  5  5  5  2  reaction  intensity set  is  is  3  nitrosyl-stretc'hing the  of  over  species  5  course  of  at  1758  absorptions  1  the  h  and of  the  3  at  2.5  H NMR s p e c t r o s c o p y  2  present  1728  characteristic  c o n f i r m e d by  5  treated  absorptions  ( T J - C H )Mo (NO) C 1 and C H H g C l a r e 5  with  s o l u t i o n at  the  being  that  readily  S  latter  This  5  C H )  surprising  ( TJ -C H )Mo (NO) C H  spectrum of  diminish  somewhat  or  3  When a THF s o l u t i o n o f  2  is  electrophiles.  end o f  the  only  reaction,  i.e.,  (T? -C H 5  5  5  )MO(NO) C H 2  3  + HgCl  > CH HgCl  2  3  + ( r } - C H )Mo(NO) C 1 5  A  possible  metel-carbon (rj -C H 5  5  5  of  centre alkyl  the  halide  This  Occupied  Molecular  the  is  at,  in  9  Orbitals  changing  is  that  the  the  iron  a result  transition (HOMO's)  (40)  metals that  requires  the  the have  are  from  mechanism  system  of  of  nitrosyl  The a c c e p t e d  and o x i d a t i o n o f ,  probably  d -d 1  2  oxidized.  cleavage  electrophile  c o m p l e x e s of  5  .  2  enhancement  in  5  S  5  the  ( T ? - C H )Mo(NO) R  more r e a d i l y  [67,69].[  for  reactivity  to  3  mercuric  attack  bond  )Mo(CO) R  complexes are for  explanation  5  metal  fact  that  Highest  metal-based  72  rather  than metal-carbon  ( 77 - C H 5  5  5  )Mo(CO) 3 C H 3  o-bond  [72],  based.  the energy  For  separation  HOMO and the m e t a l - c a r b o n  cx-bonding o r b i t a l  124  the  kJ/mol.']  However,  ( T 7 - C H )Mo(CO) 5  5  5  with,  oxidation  conditions display  relative  5  5  5  the c y c l i c  single  of  complex the  0.12 is  sec  found at  complex  which  via  possibility  is  The  of  preparation  of  salts  is  5  5  5  3  that  - 1  .  The  a  for scan  nitrosyl  fact more  This  that readily  does  not  leaves  the  bond m i g h t be t h e  metal  3  does not a p p e a r  electron  t o be the  +  site  of  complexes  with  strategy  for  complexes. This  Furthermore,  transfer dominant 2  it  abstraction  [76,77]. reaction  Since  and has  been  reactions oxidation  mode  with e l e c t r o p h i l e s ,  has  complexes  [74]  3  a-hydride  5  5  synthetic  methylene  3  ( T J - C H )Mo(NO) R 5  methyl  s y n t h e s i z e methylene  [75].  3  the M R / P h C  initial  of  the  metal.  2  5  chemistry  for  the  a useful  a p p l i e d to  5  via  at  reaction  cationic  ( T ? - C H )Re(NO) ( P P h ) C H  occur  complexes  SCE)  the  (T7 -C H )W(CO) ( P P h ) C H  suggested  identical  that  transition  of  been s u c c e s s f u l l y  S  correlate  both  to oxidize reacts  suggests  of  attack.  reaction  from  harder  0.19 V s e c  the m e t a l - c a r b o n  triphenylcarbenium the  do not  t h e peak  the  approximately  o x i d a t i o n wave. The peak  whereas  oxidation  that  electrophi1ic  ,  between  under  +1.10 V (vs  +1.67 V a t  with e l e c t r o p h i l e s proceed  - 1  3  voltammograms o f  irreversible  V  2  Recorded  t h e c a r b o n y l complex o c c u r s a t rate  is  for  reactivities  ( T? -C H )MO (NO) C H  . potential.  [73],  a  and  3CH3  example,  in it  the seems  73  reasonable  to a n t i c i p a t e  with  +  Ph C 3  might  alkylmetals,  such  abstraction  and  case,  as  that  5  (CH )„Sn,  with  3  2  form P h C C H , 3  (T7 -C H 5  )MO(NO) C H 2  5  of  Ph CR  reacting  3  + Ph CPF  3  The  organometallic  data  (p(NO):  3  5  2  5  as  chromium  is  1770 c m  + PPh  6  comparison  (Chapter  - 1  5  2  5  (T? -C H 5  5  2  (7? -C H )Cr(NO) 5  the  5  6  )Cr ( N O ) C H  5  5  2  under  these  zinc  (T} -C H 5  5  5  6  In  Ph CPF 3  6  the to  5  chloride  )M(NO) C H 2  3  with PPh  trapping  6  2  spectral (i.e.,  3  > 5  5  )Mo(NO) P P h 2  tungsten  complexes  (Chapter  suggest  to  react  + Ph CHCl  5  cation  2  with  to the  5  5  the  analogous  ( T J - C H )M(NO) C H  catalysis,  2  5  ),  The d i p h e n y l m e t h y l  complexes  (41)  5  be t r a n s f o r m e d  bond o f  3  However,  a reaction  can  3  PF .  metal-methyl  both of  indeed  unisolable.  3  with  Four)  ( T ) - C H )MO(NO) P F . 5  alkyl  (T? -C H )MO(NO) PF .  5  well  is  with  3  [ (7j -C H  as  group  i.e.,  This  > Ph CCH  6  product  1680 and  )MO(NO) P F  5  main  +  3  quickly  +  (T? -C H  of  Ph C ,  [78].  3  substrates  i.e.,  3  5  these  reactions  formation  5  of  resemble  (7} -C H )Mo(NO) C H 5  reactions  3  3  ]PF  ,  (43)  Two)  and  6  formulation reaction  41,  known  [45]  also  cleaves  (M= C r o r Mo)  as  chlorodiphenylmethane  i.e.,  > Ph CHCH 2  3  +  74  (T? -C H )M(NO) C1  .  5  5  5  2  (43)  M = Cr o r Mo  The  reaction  triarylcarbenium cleavage.  of  salts  product  coordination  PPh  5  5  5  2  2  can  to  3  3  be  5  5  5  2  + PPh  6  3  )Mo(NO) C H 2  to  2  with  5  metal-carbon  centre,  bond  occurs.  efficiently  The  trapped  by  i.e.,  > Ph CH + C H „  6  3  +  ( 7 ? - C H )Mo(NO) P F  5  abstraction  the metal  + Ph CPF  5  5  lead  hydide  organometallic  (?7 -C H )Mo(NO) C H  5  does not  Instead,  of  ( 77 - C H  2  (TJ -C H )MO(NO) PF . 5  5  5  2  6  (44)  > [ ( T ? - C H )Mo (NO) P P h ] P F  —  5  5  5  2  3  6  (45) There  is  no e v i d e n c e  coordination not  of  the  surprising  chemistry It  is  of  in S  5  5  known t h a t of  complexes  [79],  formation  of  a phosphonium s a l t  p h o s p h i n e t o an e t h e n e  (TJ -C H  insertion  for  CO i n t o  light )W(NO) B F , 2  of  the and  Lewis a c i d s  ligand.  previously  This  by is  discussed  alkenes.  s u c h as A l B r  the metal-carbon  bonds o f  3  promote  the  alkylcarbonyl  i.e.,  S  However,  this  insertion  of  strategy  is  not  NO i n t o m e t a l - c a r b o n  useful bonds,  for i.e.,  inducing  the  75  LnM(NO)R  Treatment  of  > LnM-N(0)-R.  ( T J - C H )M(NO) C H 5  5  5  aluminum t r i h a l i d e s  2  invariably  3  (M=  leads  Cr,  Mo  or  W)  to d e m e t a l l a t i o n ,  with e.g.,  AICI3  (T? -C H )Cr(NO) CH3 5  5  5  >  2  (T? -C H 5  5  5  )Cr(NO) C 1 . 2  (47) This  is  ligands  another in  metal-carbon of  d e m o n s t r a t i o n of  these  systems  the  t o enhance  ability the  of  nitrosyl  nucleophilicity  o-bonds making them more a c c e s s i b l e  electrophiles.  the  to a  of  range  76  CHAPTER  PROTONATION V S .  The p r e v i o u s alkyl, to  alkene  the  5  the  of  bimetallic  two c h a p t e r s  how t h e  5  these  reactivity  As m e n t i o n e d  [ ( 1 7 - C H )Cr (NO)  )M(NO)  5  extension  OXIDATIVE CLEAVAGE OF  and a l k y n e  ( T? -C H  of in  metal-metal  hydrides,  in  chapters,  good  ( T? -C H  hydride-abstracting  2  yields  5  U  (M  2  carbocations  =  in  reactivity  same  +  by  Mo  of  g r o u p . An of  environment.  (M= Mo o r W) of  2  bonding  containing  by t r e a t m e n t  )M(NO) H  5  5  2  ]  2  investigation  salts  5  5  an  the  [ ( 7 ? - C H ) M (NO) H ] 5  5  functional  include  bonds  5  influenced  Mo or W)  might  previous  in  describe  (M= C r ,  2  5  ligands are  studies  cations  synthesized  FOUR  the  or  the  can  be  monomeric W) ,  with  non-donor s o l v e n t s  [28],  e.g.,  2 ( 7 } - C H )W(NO) H + P h C B F 5  5  5  2  3  > [ (77 -C H ) W (NO)i H]BF 5  f l  s  5  2  2  t  + Ph CH. 3  Unlike  related  are  deprotonated  yet  not  unknown  Instead,  they  carbonyl  complexes,  by a v a r i e t y  [ ( i 7 - C H )M(NO) 5  are  5  5  cleaved  2  ]  2  to  of (M the  the  bimetallic  bases =  Mo  to a f f o r d or  W)  monomeric  1 (  (48)  cations the  as  dimers. products  77  (T7 -C H 5  5  these  5  )M(NO) H  and  2  reagents.  questions  the  5  2  to  2  well-known  protonation Initial  of  reaction  of  5  questions the  discussed. assessment  of  undergo  the  of  To 5  2  ] ?  (2)  2  the  negative  which  results  that  fully. 2  a  ]  2  This the the  way is  of also  qualitative  two d i m e r i c  oxidative  both  into  By  5  allow  the or  process?  allows  5  5  the  [28].  [ ( T ? - C H )Fe (CO)  of  Is  investigation  more  of  complexes  cleavage  under  conditions.  Section 5  5  stirred, 2  ( 1 . 0 g,  2  lightened ambient  2  ]  in  was  filtered  Celite.  The volume of  with  2.8  (0.48  2  HBF„.Q(CH ) 3  red-violet mmol) mL,  colour.  temperature  solution  2  dark  3  at  two  analogous  indicated  with HBF„  2  protonation  13.6 M H B F « . 0 ( C H )  stirred  ]  of  5  5  solution  2  propensities  [ (r3 -C H )Fe(CO) ] 5  in  answered  [ ( T ? - C H )Fe (CO)  a  the  reversible  regard  combined  experimental  Reaction  be  a  detailed  5  either  Experimental  dimer  this  protonation  The  5  5  more  to  Can  5  [ ( 7 ? - C H )Cr (NO)  comparison,  added  a  observations,  [ ( T 7 - C H )Cr (NO)  in  by  be p r e p a r e d by p r o t o n a t i o n  answered  5  these  = base)  (B  +  2  (1)  chromium  c o u l d be  )M(NO) (B) ]  of  cation  +  the  describes  these  H]  5  mind.  dimer,  chapter  to  fl  experiments  questions  above  5  light  came 5  5  In  [ ( 7 j - C H ) C r (NO) 5  [ (77 -C H  filtrate  mmol)  2  whereupon  reaction  ( 2 x 3  was  of  (30 mL)  cm)  was the  mixture  30 m i n , and the  through a short the  2  The  for  solution  in CH C1  6.5  2  was  final  red  column  of  reduced to c a .  15mL  78  in  vacuo,  and d i e t h y l  resulted  in  [ (T? -C H  ) Fe  5  5  the  2  5  2  Found:  C,  (CO) „ H ] B F  (s)  cm" .  1H,  Fe H).  1  1  C  2.52.  0.54  added.  This  g (43% y i e l d )  as a r e d - v i o l e t ,  1 4  H  Fe O  1 1  2  i (  BF :  crystalline  2  38.07; 2068  v(CO)  2  6 5. 32  2  C,  a  IR(CH C1 ):  H NMR ( C D C 1 ): 2  of  then  of  solid  filtration.  for H,  4  was  (s,  2.51.  (s),  10H, C H ) , 5  H,  2045  -26.61  5  (s,  2  Reaction A [22]  of  M  colour and  5  5  g,  the  sharp  amount  the  mixture  was  and  then the  The n a t u r e  this  dark  employed  in  green the  Procedure dryness  in  with H 0  (3  2  mmol)  in  at  the  The  x 10 m L ) . 2  dark  (15  of  [ (rj -C H 5  precipitated.  1728  cm" . 1  was  depended on t h e  dark and t h e  was  2  with the  An  IR  strong,  The  reaction (2  x  reduced to c a . isolated  work-up  3 10  from  procedures  below.  green  filtrate  resulting  A solution  ]  two  Celite  products  2  green-brown  exhibited  filtrate  )Cr (NO)  5  whereupon  to  t h r o u g h a c o l u m n of the  2  treated  mmol),  solid  and  5  was  changed  organometallic  mL)  3  1.2  solution  manner d e c r i b e d  vacuo,  H 0  of  HBF„.Q(CH )  (25 mL)  2  mL,  1838  filtrate  A.  with  immediately  filtered  of  2  2  of  volume  ]  in C H C 1  supernatant  absorptions  2  solution  (0.09  2  solution  small  spectrum of  )Cr (NO)  0.60 mmol) 3  of  5  red-violet  HBF„.(OCH )  a  cm),  [ ( T? -C H  stirred,  (0.21  13.6  mL.  by  Calcd 37.77;  (40 mL)  precipitation  w h i c h was c o l l e c t e d Anal.  ether  of  slowly  was  residue NaBPh„  added t o  taken  was (0.60  the  to  extracted g,  extracts  1.7 to  79  induce The  the  formation  a finely-divided  s o l i d was c o l l e c t e d  10  mL),  and  Recrystallization  green-brown  in  of  solid  (vs)  C H ), 104°  cm  - 1  5.60  5  (3  2  (5  x  10~  mm  3  x  Hg).  from C H C 1 - h e x a n e s p r o d u c e d 2  )Cr (NO)  5  5  5  precipitate.  washed w i t h H 0  vacuo  (T? -C H  for  .  C  2 3  2  2  (OHBPh )  as  C,  H,  3  H ,CrN 0 B: 2  2  63.23;  H,  4.77;  1714  (vs)  cm  1813 ( s ) ,  1712  this  of  Calcd  Found: C,  v(HO)  filtration,  yellow  a  fine  powder.  Anal. 6.42.  by  dried  0 . 1 6 g (31% y i e l d )  6  of  'H NMR  (s,  - 1  3  N, .  6.37. 2  5H,  C H ), 5  5  2  5  3.13  2  v(HO)  1H, O H ) .  N,  mull):  1823  7.51-7.04  (s,  4.85;  IR(Nujol  IR(CH C1 ):  ((CD ) CO): 3  63.33;  (m,  (s), 15H,  Mp ( i n  air)  dec. Procedure  solid was  B.  [PPN]Br  stirred  The d a r k  (0.76  for  g,  T5  under  extracted  with  extracts  were f i l t e r e d  Florisil the  reduced (C H ) 0  was  concentration  of  crystallization 5  5  5  5  (3  2  filtrate  mmol),  Volatile  )Cr (NO) B r 2  components  x 15 m L ) .  The  combined,  spectroscopic  by  0.19  properties  frit.  addition solution  g  was  ( 2 x 3  (63%  identified  with those  of  of  with  mixture  were  the  through a short  which  resulting  and  resulting  of  treated  pressure,  doubled  the  was  and the  s u p p o r t e d on a m e d i u m - p o r o s i t y  filtrate  (T7 -C H  1.2  min.  removed  2  green  then  residue  cm)  was  golden  column o f  The volume hexanes.  in vacuo  induced  yield)  of  of Slow the  golden  by c o m p a r i s o n of an a u t h e n t i c  its  sample  [86]. IR(CH C1 ): 2  2  v(NO)  1819 ( s ) ,  1713  (vs)  cm" . 1  1  H  NMR  80  (CDC1 ):  6  3  (probe  5.75  temperature  ([P-2NO] ), +  (s, * C H ) . 5  Low-resolution  5  8 0 ° ) : m/z 256 ( P ) , +  226  mass  ([P-NO] ), +  131 ( [ P - 2 N O - C H ] ) , 117 ( [ P - 2 N O ~ B r ] ) . 5  5  +  spectrum  +  196  81  Results  and D i s c u s s i o n  I)  [  (T? -C H  )Fe(CO)  5  5  5  published observations behaviour  of  the  [80,81,82] 3  5  5  5  yields,  2  ) Fe 2  2  (CO)  2  ] . -  In  2  other  iron  in CH C1  2  investigators  dimer  in  of  [  results  flH]BF„  accordance  5  5  in  which  the can  5  5  )Fe(CO)  5  2  + HBF, . 0 ( C H )  2  3  5  spectroscopic  air-sensitive cm  - 1  .  ]  2  the  media with  2  formation  isolated  in  of good'  2  [ (T] -C H ) Fe (C0) „H]BF  The  protic  clean be  the  concerning  strongly  (T? -C H  with  i.e.,  [ (r? -C H )Fe(C0) ] 5  of  treatment  HBF„.0(CH ) [ (TJ -C H  2  'H NMR ( C D C 1 ) :  Fe H)] 2  are  2  consistent  on a v e r a g e ,  5  2  2  properties  complex 2  5  of  [IR(CH C1 ): 2  5 5.32  (s,  w i t h the  the m o l e c u l a r  2  this  v(CO)  bimetallic  + 0(CH ) 3  2  (49)  red-violet,  2 0 6 8 , 2 0 4 5 , 2008  10H, C H ; 5  0  5  -26.61  (s,  1H,  cation possessing,  structure  i?C& CO OC-Fe-H-Fe-CO  Its  'H  NMR  spectrum does not  exclude  the  possibility  that  82  the  closed 3-centre-2-electron  bent  in  the  instantaneous  spectrum does suggest a mixture  of  Reaction cation  (49)  of  (C H ) N.  This  solutions  of  2  the  5  is  Lewis  3  addition  reaction  HBF„  in  a  5  of  5  as  2  a ]  5  2  immediate  conversion  by  1512  Concomitantly, nitrosyl  cm  new  ligands  an e q u i m o l a r  reaction  - 1  mixture  as  [ (i? -C H ) F e 5  2  (CO) „ H ]  2  dimer  previous  a  [80]  or  report  virtually  that  unchanged by  =  5  )Fe(CO) L ] 2  another  oxidant  successfully  of as  5  5  absorptions  of  the  diminish  of  acid  has  appears  to  contain  or  2  3  ]  to  solution  reactant  the  strong at  1667  intensity. to  1838 and been  of  the  in  to'  2  results  2  by t h e  attributable  amount  2  that  the  at  H 0  f t  progress  reveals  grow  dimer  HBF .O(CH )  5  and  of  [84,85].  evidenced of  light  in a d d i t i o n  [ ( 7 j - C H )Cr (NO)  a b s o r p t i o n s due t o gradually  +  +  by  (L  5  Monitoring  appear  5  neutral  2  solution  5  iron  spectroscopy  nitrosyl-stretching  complex e x i s t s  the  reaction,  IR  IR  why o x i d a t i o n s o f  require  2  2  be  its  in  5  5  CH C1  However,  Furthermore,  [ (rj -C H  t o be e f f e c t e d  5  well  aqueous a c e t o n e  are  2  HBF„.  clear  to  becoming green-brown.  After  5  is  the  [ ( 7 ? - C H ) C r ( N 0 ) ] . The a d d i t i o n  an  and  such  aqueous it  the  parent  explains  species  red-violet  in  the  [ ( T 7 - C H )Fe (CO)  order  II)  to  bases  in aqueous acetone 2  solution  reversible,  fact  (49),  7? -alkene)  in  [83].  may  [82].  being converted  variety  linkage  structures  that  rotamers  Fe-H-Fe  terminal 1728 c m  added,'  approximately  - 1  .  the  equal  83  amounts of species.  the  Addition  completely  the  concentration Similar reaction Again, two  reactant of  of  the  5  new  CD N0 ) 3  are  s p e c t r u m of region  this  characteristic  position  of  downfield  from t h a t  4.89).  This  this  observed  consistent cleavage  [ (r5 -C H 5  5  with  )Cr(NO)  2  containing  acid  consumes  1 2 and d o u b l e s  5  5  (6  there  of  dimer  final  6.03)  in  of  is  the  the  product. resonance  is  in  5  5  electron  former  (T7 -C H 5  5  given  5  2  )Cr (NO) B F „  the  ]  2  (6  2  density  on  reactants  a  and  product  simple  the are  oxidative  i.e.,  it 2  the  species.  the  of  the  considerably  5  less  The  However,  organometallic  occurrence  mixture  [ ( T 7 - C H ) C r ( NO)  of  the  requires  reaction  protons.  5  of  + 2 HBF „  > 2 (T J - C H 5  5  s  )Cr (NO) + H  Unfortunately,  the  H NMR s p e c t r o s c o p y .  a singlet  T7 -C H  ligand  1  course  organometallic  displays  that  the  ]  the  stoichiometry  reaction,  5  and  of  properties  2  nitrosyl  characteristic  indicates  spectroscopic  the  resonance  cyclopentadienyl The  )Cr (NO)  of  made when t h e  one  mixture  5  m o n i t o r e d by  acid,  predominantly  equivalent  5  complete consumption of  contains  nitrosyl-  species.  is  2  of  new  [ ( 77 - C H  observations  (in  the  a further  remaining  equivalents  the  and  has  been  impossible  p r o d u c t as  observations  described  such. in  This  to is  previous  2  2  isolate not  BF„ (50)  the  surprising  chapters  and  84  the  recent  generated CH N0 3  report by  [45].  2  the  HBF .0(CH ) a  (T7 -C H 5  5  3  50  weakly 3  viscous,  in  [ (T7 -C H 5  2  is Scheme  II)  For  oil.  clean 5  of  which  6  (rj -C H 5  of  5  3  2  may  )Cr (NO) C H  s  2  it  the  or C D N 0  2  )Cr (NO)  5  the  also  can  be  methyl  affords  organometallic  supported which  instance, of  be in  3  verified precursor  solutions  of  product  in  solvent  3  of of  [88]  + CH CN 5  solutions  of  of  5  5  group  from C H , C 1 2  produces  1)  this  oil  the  previously  5  )Cr (NO)  solid  ( T J - C H )Cr (NO) B F 5  BF„  i n CH CN  2  a  results  3  prepared  >  3  addition  2  evidence  i.e.,  5  the  the  removal  5  5  [ (TJ -C H  Furthermore,  that  5  (CH CN) ] B F „ ,  2  chemical  ( T ? - C H )Cr (NO) B F  formation 2  by  indicates  Dissolution  (T? -C H )Cr(NO) B F „ 5  of  treatment  solutions  2  green  the  5  2  analogously,  in C H C 1  2  ligated.  CH N0  5  that  )Cr (NO) P F  5  protonation  formulation  (summarized  in  5  2  reaction  or  5  )Cr (NO) B F „ .  5  The  is  ( 77 - C H  Completely  spectroscopically with  of  2  4  2  ( C H C N ) ]BF, . 3  [PPN]Br  initiates  to the  (51 )  CH C1 2  2  metathesis  reaction  (T? -C H 5  5  5  )Cr (NO) B F 2  f l  + [PPN]Br  > (rj -C H 5  5  5  )Cr (NO)  2  Br  + [PPN]BF  a  (52)  to  &  X  CD X  Q. CD  o o  O X O  «  Lu LP  X JO  X  CM  eg  0 N  X CM  X  a CD  c  O  c5  X  CM  u c CD  CD X  10  o o CM  o  CJ  z  Ho X CJ  X m  »  X to O  86  from w h i c h  the  well-known  may be c o n v e n i e n t l y Attempts 50  to  isolated isolate  have a f f o r d e d o t h e r  [29].  Thus,  mixture  not  ( T j - C H ) C r (NO) B F „ 5  5  but  5  rather  results  [ { ( T ? - C H )Cr (NO) } 5  solid  5  2  2  reaction  to  50 a s  solutions 5  5  (r7 -C H  ( 77 - C H 5  5  5  yields.  complex  2  )Cr (NO) B F „ 2  5  to  2  the  the  reaction  of  chromium  the  deposition  5  5  a dark  final  reaction  precipitation  [ ( T? -C H ) Cr (NO) 5  from  complexes  even  isolate BPh„~  result  salt  3  )Cr (NO) B F „ 2  the  in  2  (0 ( C H ) } ] B F „ 2  low  green,  of  5  2  yields  of  microcrystalline  + H 0  as  one o f  heterolytic by B P h „ ~ ,  in  metathesis  in  the  of  aqueous  formation  of  > PhH + B F « ~  ( T J - C H )Cr (NO) 5  5  5  complex b e i n g  steps.  of  i.e.,  ligand  cleavage i.e.,  by  It  in  2  (OHBPh ) ,  in  5  5  certainly  preformed  does  [ { (rj -C H 5  moderate  deprotonation  [ ( r j - C H ) C r (NO) 5  (53)  3  isolable  53 p r o b a b l y p r o c e e d s v i a  aquo its  product  + BPh„"  2  organometallic  Conversion  organometallic  instead  2  coordinated a  5  in  O H ] B F „ as  its  5  final  BPh "  5  2  +  a  )Cr (NO) B r  5  63% y i e l d .  result  ( 77 - C H ) C r ( N O ) ( O H B P h ) ,  the  5  [29]. Attempts  5  in  (C H ) 0  in  5  5  of  or  2  (rj -C H  new n i t r o s y l  addition  does  [87]  5  5  2  (OH ) ] 2  not )Cr (NO)  +  of by  involve 2  } OH] 2  +  87  [{(T} -C H )Cr(NO) } OH] 5  5  5  2  2  + BPh„~  +  +  since two  it  has  been e s t a b l i s h e d  reactants  experimental  [ {(TJ -C H  conditions,  )Cr (NO) }  5  5  engage o n l y  2  5  2  in  > (r? -C H 5  5  s  )Cr (NO)  2  (T? -C H )Cr(NO) (OHBPh ), 5  5  5  2  independently  (54)  3  [29]  simple metathesis  that  these  under  these  i.e.,  OH]BF  + NaBPh„  ((  > NaBF,  +  [ { ( 77 - C H ) C r ( N O ) } O H ] B P h . 5  The new  complex,  other  ( TJ -C H  have  monomeric,  5  5  structures IR  5  spectra  (in  d -acetone)  in  s o l u t i o n and t h e  expected  1818 and  ligands.  C H 5  5  (6  ca.  signals  Cr 0  resembles  3  have  been shown  and  3  its  solid  display  cm 1  whose  - 1  due  OH  protons,  (6  two to  H NMR s p e c t r u m to C H  H  BPh  state  1713  to  molecular  attributable  for  >  (OHBPh ) ,  solid  (55) '  a  air-stable  Furthermore,  5.60),  2  piano-stool  a green-brown,  ca.  2  which  is  c o n s i s t s of  6  7.51-7.04),  species  It  nitrosyl  2  5  three-legged  s t r o n g a b s o r p t i o n s at terminal  5  5  2  both  5  ( 7 j - C 5 H )Cr (NO)  )Cr (NO) X  [26].  Ph  3.13)  6  S  (8 as  88  which  involves  interaction. s t r o n g as of  However,  fragmentation  entities,  the  These  parent  results  b e g i n n i n g of  [ ( 7 } - C H )Cr (NO) In  5  5  addition,  isolated  HPF  5  )Cr (NO)  5  does  6  this  not  ]  only the  that  can  correspond  to  nitrosyl  complexes  of  Possibly,  the  species  to  be  Protonation  the  [ (T? -C H 5  5  acid  resulting and  two q u e s t i o n s  that  the  base  2  been any  in  the  the  at of  negative. solid  solutions  2  chromium d e s c r i b e d requires  protonation  treated  of  posed  unidentified  CH C1  of  w i t h HBF „  and  organometallic in  this  an e x c e s s o f  5  )M(LO) 3  products.  2  A  experimental reaction  2  ]  2  in  results  ( M = Cr o r CH C1 2  possible  one  Fe;  is  chapter.' the  acid  is  clear  in  i.e.,  might  C)  of  dimers  different for  that  It  treatment  L = N or  followed  pathway  Cleavage.  the  explanation  being  (protonation),  that  results  2  observations  pathways are  instance,  transfer  Versus Oxidative  preceding  HBF„.0(CH )  For  ions  specrum  present. Ill)  from  the  had  particularly  detectable.  from  which  former  due t o  i n d e e d be a n s w e r e d  indicates  acid-base  70 eV mass  c o n c e r n i n g the  [28]  2  the  not  individual  verify chapter  Lewis  is  signals  being  work  2  that  ion not  previously  [ ( 77 - C H 5  ]2  linkage  fact  of  this 2  hard-hard  this  complex d i s p l a y s  from t h e  5  relatively  e v i d e n c e d by t h e  the  the  a  entirely  d u r i n g the involve  with  types  these  the  of  varied different  conversions.  initial  proton  89  [ (V-C H )M(LO) ] 5  2  5  + H  2  > [ (r? -C H )M(LO)  +  5  5  5  ] H  2  +  2  (56)  whereas  another  might  cleavage)  as  [ (T> -C H  )M(LO) ]  5  S  5  the  2  have  first  step,  + 2H  2  electron  transfer  (oxidative  i.e.,  > 2 [(T? -C H )M(LO) ]  +  5  + H .  +  5  5  2  2  (57)  In  other  words,  behaviour be  of  a  the  to  supported at  possible that  organometallic  first  glance  readily  that  the  cleaved  [ (T? -C H 5  5  proceeds dimer  5  s  )Cr (NO)  benzylic  ]  2  ]  2  and  2  + PbCl  in  organic  d o e s not  halides  Furthermore,  towards  This  view  the  5  5  Thus, while  5  2  ]  with P b C l  the  5  2  iron 2  ]  be  which  2  is  is  more  reaction  )Cr (NO) C 1 2  [ 2 3 ] . In  dehalogenates the  to  2  t e t r a h y d r o f uran.,  [ ( 7 ? - C H )Cr (NO) 5  different  chromium d i m e r  5  whereas  simply  seems  5  complex  may  +  documented c h e m i s t r y  > 2 (T? -C H  2  chemical  intrinsically  5  react  5  H  [ ( r j - C H ) C r (NO)  refluxing  chromium  different  by p r e v i o u s l y  C r - C r bond i n  cleanly  the  their  by e l e c t r o p h i l e s .  apparently  fashion,  2  the  dimers  oxidation.  5  5  of  undergo  [ ( T ? - C H )Fe(CO)  indicates  [24].  is  manifestation  tendencies  of  it  + Pb  (58)  the  iron  similar  vicinal  compound d o e s  or not  oxidized rapidly  90  (10 min)  [ (TJ -C H  by two  5  5  5  equivalents  )Cr(NO)  ]  2  + 2 Ph CBF  2  3  2  w h e r e a s when [ ( 77 - C H 5  approximately only  slowly  properties have  of  the  5  having  5  9  )Fe(CO)  V 5  5  experimental of  cannot  undergoes context  57,  of  is  2  - 1  .  5  the  it  5  5  should  the  of  [89].  3  45 h  exhibits  2  the  of  E(pa)  at  H  +  2  clear  a  more p o s i t i v e being  the  ]  in  CH C1 2  cleavage  2  same rate  E(l/2)  potential.  In  the  here,  this  strong oxidant  sufficiently of  the  of  a c c o r d i n g to  be  of  chromium complex  considered  a sufficiently  certainly  same o x i d a t i v e  that  rate  a scan  comparison  is  = +0.68 V  isoelectronic  b e i n g +0.85 V a t  direct  data  electrode  a scan  the  is 2  redox  voltammogram  with E(1/2)  100 mV a t  is  electrolyte,  a cyclic  contrast,  it  with  complex  about  supporting  reversibility  reactions if  treated  o x i d i z e d i r r e v e r s i b l y ' under  be made,  that  is  Ph CBF„,  information  Although a  the  of  2  a p l a t i n u m bead  In  [ ( r ? - C H ) C r (NO)  then  effect  .  2  course  separation  oxidation  indicates oxidize  ]  2  of  CH C1  n  the  conditions,  0.077 V s e c  values  - 1  i  Thus at  2  sec  [ ( 7 7 - C H )Cr (NO) 5  ]2  (59)  3  some e l e c t r o c h e m i c a l  ] 2 in C H C 1  2  + 2 {Ph C},  a  dimers,  as  6  and a peak  0.067  the  [90].  a h i g h degree  SCE)  2  2  equivalents  acquired 4  5  5  5  reactant  (n-C H )«NPF  [ ( 77 - C H  (vs  three  >  a  5  )Fe (CO)  5  i.e.,  3  some q u a l i t a t i v e  been  with  5  Ph CBF„,  ( T ? - C H )Cr (NO) B F  consumed o v e r  To g a i n  of  equation potent  [ ( i 7 - C H )Fe (CO) 5  5  5  to  2  to ] 2•  91  The  fact  that  (equation  56)  the  suggests  [ ( T 7 - C H )M(LO) ] 5  2  involving  unified  2  basis  of  rationale  adduct  is  5  5  )M(LO)  adduct  isolable  ]2  2  may  (as  with transfer  to  as  be  case  of  [ ( T ? - C H )Cr (NO) 5  5  5  2  ] H 2  data,  another  stable  dissociation.  5  5  For  neutral latter the  hydrido complex  original  recycling (TJ -C H 5  5  5  of  is  thermally  unstable  dimeric  5  5  5  5  reactant  conversions 2  observed  could for  2  +  5  55 simply  ( 77 - C H 5  5  >  5  2  instance,  +  +  5  2  H,  (60)  the  )Cr (NO) H . However,  this  2  +  2  [25]  and c a n  thus  allowing  and  60.  )W(NO) H 2  (T? -C H 5  5  5  to  sequential  in  [28],  )Cr (NO)  revert  Alternatively,  be p r o t o n a t e d 5  the  p r o d u c t and  5  (T? -C H  ( 7 } - C H )Cr (NO) H + H 5  5  complex,  )Cr (NO) H  previously  5  be  i.e.,  5  ( T 7 - C H )Cr (NO)  56.  to  Alternatively,  > ( r ? - C H )Cr (NO)  ultimate  of  summarized i n e q u a t i o n  5  the  more  cationic  ( 77 - C H ) C r ( N O )  would a f f o r d  as  2  step consists the  such d i s s o c i a t i o n ,  +  2  the  simplistic.  M = Fe).  case  of  in CH C1  2  sufficiently  in  M = Cr,  too  produce  may u n d e r g o u n s y m m e t r i c a l of  3  available  adduct the  is  instead  reactions  4  species  the  the  HBF .0(CH )  to  H +  simply protonated  p o s s i b l e . The f i r s t  prove in  is  viewing  currently  formation  t ( 77 - C H This  that  simple electron  Ori t h e  5  dimer  dimers  5  5  iron  manner  i.e.,  + 2  the  +  H . 2  (61 )  92  CHAPTER  FIVE  EPILOGUE  The  research  thermally  described  unstable  organometallic synthesis  of  compounds  the  organic 5  5  similar  different  Three  shown t h a t  both  and  seems c l o s e r  the  group  metals.  significant  [ (T] -C H 5  5  5  )M(LO)  electrophiles.  2  ]  2  5  =  a  this  Lewis  described 5  that  electrophiles. displayed  The  results in or  Fe,  acid  by  the  similar  in  Chapter Cr)  react  with  Again,  this  complexes  N  with is  Four  reactivity =  its  for  in Chapter  L  that  (M = Mo o r  2  nucleophiles  complex  reactivity  observed  that  Cr  of  This  5  conditions.  established  is  that  differences (M  has  the  2  ( 7 ? - C H )M(NO) R  organic to  5  reactivity  The work  organometallic  versatile  experimental  3  stable  reactivity  shown  5  the  )W(NO) - c o n t a i n i n g  5  A1C1 . from  a  that  be e m p l o y e d f o r  (T? -C H  entity  +  complexes.  inorganic  main  2  to  metal  complexes are  of  can  substrates  )W(NO)  transition has  that  shown  is  2  characteristic  5  significantly  5  appropriate  ( T? -C H  reactivity  5  variety  with unsaturated component  5  electrophile a  Two has  ( r ? - C H )W(NO) B F „  under  Furthermore,  in Chapter  or  0)  of have of with  93  the  T h e r e must be some f u n d a m e n t a l  reasons  which  explain  chemical  organometallic  nitrosyl  complexes  and  discussion is  far  differences their  on  the  beyond t h e  compounds  carbonyl  electronic  s c o p e of  utilized  in  are  In  fact,  directly  here. the  In  to  dicarbonyliron  a  certain  fragment  amount  Fe(CO)  5  taken  2  by  complexes  is  5  be 2  accompanied  metal-CH  3  cr-bond i n whereas  been  study  described  to  energies  (UPS)  that  results  delineate  of  these  bond the for  perturbation  2  replacing With  results  comparison  the  ( r j - C H ) C r (NO) C H  91.  The  5  the  5  5  This  3  a  2  valence  stabilization  are  ionizations.  5  For  data  5  as  these  those  3  of levels  dn  destabilization  in  the  metal-carbon  i r o n compound is- 1 40-kJ/mole • below t h e chromium compound t h e  II)  2  metal  the  for  )Cr (NO) C H  to  example,  levels  for  5  of  a  (Table  3  (T? -C H  compared  pronounced  UPS  analysis  i o n i z a t i o n s or  "compressed"  by  of  on m e t a l  and  )Fe(CO) C H .  5  in  has been made  trepidation,  a  shows t h a t to  ( 77 - C H 5  3  from r e f e r e n c e  appear  have  by a d i n i t r o s y l c h r o m i u m o n e .  to Cr(NO)  2  (rj -C H )Fe(CO) CH 5  of  the  below.  c a n be e v a l u a t e d 5  the e x p e r i m e n t a l  electronic  of  Spectroscopy  related  an a t t e m p t  complexes  some  chapters  the c o n c l u s i o n s reached  a  The  previous  complete  these  However,  Photoelectron  on t h e m o l e c u l a r  summarized  work.  of  A  some of  particular,  effect  analogues.  structures  this  the  a n a l y z e d by U l t r a - V i o l e t [91].  between  difference  the is  HOMO,  reduced  94  to  94 k J / m o l e .  Cr(NO)  Thus,  group,  2  in changing  the  metal  localization  onto  density  destabilized  is  largely  in  accounts  the  the  Cr)  density  dir  nitrosyl  ligands  by t h e  vicinity  for  (M = Mo o r  the  from a F e ( C O )  of  higher  of  reactivity  of  the  attack  the  accomodate  reactivity  of  (T7 -C H  bond  that  is  very  for  ( T? -C H  metal-hydrogen electrophilic  attack  The H e l / H e l l ( T? -C H 5  5  5  establishing M(CO)  group  2  difference marked  is  81  For  the  reduced  to  the  separation  5  that  by a M ' ( N O )  is  . For  the  chromium complex  the  average  complex,  kJ/mole.  probably  even  occupied  position  the  c o m p l e x e s has  studies.  in  has  a to  greater  been p u b l i s h e d  resolution  of  for  when  the  there 'd'  is  a  level  in  this the  C r - C l ir*  'd*  level  congener  UP s p e c t r a  using  level  separation  tungsten  and a s s i g n m e n t  However,  useful  this  [63].  and  significant  analogous  Furthermore,  2  differences  that  highest  the  some  also  2  levels  the  ( T 7 - C H )Cr (NO) C 1 . A c o m p a r i s o n of  two n i t r o s y l  can  )Fe (CO) C 1  of  carbonyl  5  5  group. A  2  the  5  towards  It  is  ir  metal  in  5  is  2  susceptible  5  two compounds  below  76  5  which  2  data  on t h e  replaced  complex  kJ/mole  levels.  two  is  stabilization  nitrosyl  of  effects  between  the  is  the  analyses provide  2  bond.  )W(NO) H ,  5  5  [25].  UPS  )Cr (NO) C 1  5  description 5  electrophilic  5  remains  analogues  metal-carbon  a  3  ( 7 j - C H )M(NO) R  over  the  carbonyl  a by  M-CH  and  This  complexes at  the  charge  metal.  to  stabilized  while  loss  the  is  group  2  of  the  There  are  between  the the  95  Table  II.  Results  for  Peak  He(I)  and  He(ll)  ( T J - C H )Fe(CO) C H  Valence  5  5  5  2  I.E.  3  5  He(ll)  Area  Area  ( r 5 - C H )Fe(CO)  A  7.71  B  7.97  C D  5  5  CH  5  2  A%  3  43  8.51  0.12  0.14  17  9.17  0.25  0.19  -24  5  A  7.93  B  8.18  C D  5  )Cr (NO) C H 2  3  0.28  0.37  32  8.65  0.15  0.21  40  8.91  0.18.12  Bands A ,  B,  -33  and C a r e m e t a l  Band D i s m e t a l - C H  3  a  level  (eV) 3  Hed)-He(ll)  0.33  5  Assignment:  2  5  0.23  (T7 -C H  Analysis  and ( T ) - C H )Cr (NO) C H  He(I)  5  Band  'd'  levels  96  assignments highest  discussed  occupied  approximately  above,  the  separation  level  and  the  'd'  85 k J / m o l e .  stabilization  on  the Dewar-Chatt-Duncanson  bonding.  The  scheme, a s  components:  (a)  overlap  o-type  the  acceptor  resulting orbitals effect  remaining  6ir  density  electron  5  2  w i t h the  a  of  the  empirical  that  the  metal  is  a  This  irThe  to  complex  a-donor  reached  of  with  make  interaction  strength.  conclusion  consists  carbon atoms.  alkene  by  a "back-bond"  dir d e n s i t y  for  level  metal-alkene  olefin  (b)  is  seen  from f i l l e d  on t h e  stable  bond  the  'd' be  for  and  density  available  system r e q u i r e s  the m a j o r i t y  of  s t a b i l i z e d metal  Thus,  can  model  on t h e m e t a l ;  density  ligands.  5  agree  of  strongly  ( T ? - C H )W(NO) supply  orbital  this  the  levels  TT*  d e p i c t e d below  into antibonding o r b i t a l s  metal  5  loosely  ir-electron  from f l o w  of  less  of  of  complexes  reviewing  two  W-Cl  The c o n s e q u e n c e  metal-alkene  between  with in  the  interaction seems  in Chapter  to  Two.  97  REFERENCES AND NOTES (1) Cotton, F.A.; Wilkinson, G. 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Geiger,  W.E.  J^  Chem.  100  (52) Collman, J.P.; Hegedus, L.S. "Principles and Applications of Organotransition Metal Chemistry", U n i v e r s i t y S c i e n c e : M i l l V a l l e y , C a . , 1980. (53) 1981,  Sunkel, K.; 166, C 9 .  Nagel,  U.?  Beck,  (54) S a m u e l s , S.-B.; Berryhill, O r g a n o m e t . Chem. 1 9 7 9 , 166, C 9 .  W.  S.R.;  (55) (a) Woodward, R . B . ; H o f f m a n n , R. E n g l . , 1969, 8, 7 8 1 . (b) Dewar, M . J . S . E d . E n g l . 1 97 1 , 10, 761 . (56) Halpern, Volume I I " , I. Y o r k , 1977.  O r g a n o m e t . Chem. Rosenblum,  J . In " O r g a n i c S y n t h e s i s v i a M e t a l C a r b o n y l s , Wender, P. P i n o , E d . , W i l e y - I n t e r s c i e n c e : New  H e i m b a c h , P.  Angew.  (58)  Snider,  B.B.  A c c . Chem. R e s . 1980, 1 3 ,  (59)  Scheck,  D . ; R o s e n b l u m , M. O r g a n o m e t a l l i c s  Chem.,  Hanack, M.; Harder, 1981 , 2 2 , 5 5 3 .  (61) L u k a s , Chem. , I n t .  J.  Angew. Chem.' I n t . E d . Angew. Chem., Int.  (57) 976.  (60) Lett.  M.  I.;  Int.  Ed.  Engl.  Bofinger,  1 9 7 3 , 12,  426. 1982, 1, 3 9 7 .  K.-R.  J . H . ; Baardman, F. ; Kouwenhoven, E d . E n g l . 1976, 6j_ 3 6 9 .  Tetrahedron A.P.  Angew.  (62) S i m i l a r b e h a v i o u r has been o b s e r v e d t o o c c u r d u r i n g t h e reactions of the i s o e l e c t r o n i c ( T J - C H )Re (CO) ( N O ) C l w i t h P h L i o r PhMgBr: S w e e t , J . R . ; Graham, W.A.G. Organomet. Chem. 1983, 2 4 1 , 4 5 . 5  (63) Morris-Sherwood, B.J.; I n o r g . Chem. 1 9 8 1 , 20 , 2 7 7 1 .  5  Kolthammer,  5  B.W.S.;  (64) N e g i s h i , E. "Organometallics in Organic Volume I", J o h n W i l e y a n d S o n s : New Y o r k , 1 9 8 0 ,  Hall,  M.B.  Synthesis, pp286-393.  (65) (PhCH ) Sn is b e s t s y n t h e s i z e d from ( P h C H ) S n C l and P h C H M g C l i n THF r a t h e r from S n C l „ a n d PhCH MgCL directly since the latter reaction is often accompanied by t h e f o r m a t i o n o f s u b s t a n t i a l amounts o f b i b e n z y l . 2  f l  2  2  (66) F a l l e r , 3398. (67)  3  2  Dizikes,  J.W.; L.J.;  Shvo,  Y. C  Wojcicki,  Am.  Chem.  Soc.  1 9 8 0 , 102,  A . J ^ Am. Chem. Soc•  1977,  99,  101  5295. (68) Piper, 3j_ 104.  T.S.;  Wilkinson,  G.  Inorg.  N u c l . Chem. 1956,  (69) F o r an o v e r v i e w of this and similar reactions see Kochi, J.K. "Organometallic Mechanisms and Catalysis", A c a d e m i c P r e s s : New Y o r k , 1978. (70) B e a c h , D . L . ; D a t t i l o , Chem. 1977, 140, 4 7 .  M.;  (71)  King,  Bisnette,  (72)  Green,  Jackson,  R.B.; J . C ;  Barnett,  K.W.  J^  M.B.  Inorg.  Chem.  S.E.  J_;_ Chem. S o c .  Organomet.  1964, 4,  486.  1976, 1698.  (73) Legzdins, P.; W a s s i n k , B., u n p u b l i s h e d o b s e r v a t i o n s . The measurements were made on C H C 1 s o l u t i o n s t h a t were 5 x 10 " M in the organometallic complex and 0.1 M in (n-C H )«NPF . 2  2  -  a  9  6  (74) K e g l e y , S . E . ; 1982, 760.  Brookhart,  (75) Wong, W.-K.; 1979, 101, 5 4 4 0 . (76) H a y e s , 5570.  J . C ;  Tarn, W.;  M.;  Husk,  Gladysz, J.A.  Cooper, N.J.  Organometallics  J ^ Am. Chem.  J ^ Am. Chem. S o c .  (77) K i e l , W.A.; L i n , G . - Y . ; Bodner, Am. Chem. S o c . 1983, 105, 4 9 5 8 . (78) O.A.  G.R.  G.S.;  I.P.;  (81) 953.  Symon, D . A . ;  (82)  Harris,  D.C;  Waddington, Gray,  H.B.  W.;  T.C  Pratt, J_;_  Inorg.  L.;  Chem.  Chem.  R.E.; 102,  Wilkinson, Soc.  1975,  J.  Reutov,  S.B.; Strauss, S.H.; H o l t , E.M.; Stimson, S h r i v e r , D . F . JL Am. Chem. Soc. 1980,  (80) Davison, A . ; . McFarlane, J . Chem. S o c . 1962, 3 6 5 3 .  104,  Gladysz, J.A.  K a s h i n , A . N . ; Bumagin, N . A . ; B e l e t s k a y a , Organomet• Chem. 1979, 171, 3 2 1 .  (79) Butts, A l c o c k , N.W; 5093.  1982,  Soc.  14,  A  G.  1971, 1 215.  (83) P e t e r s e n , J . L . ; Brown, R . K . ; W i l l i a m s , J . M . ; M c M u l l a n , R . G . ; I n o r g . Chem. 1979, 18, 3493 and references cited therein.  1 02  (84) 345.  Dombek, B . D . ;  (85) 114,  Boyle, 307.  Angelici,  P.F.;  R.J.  Nicholas,  Inorg•  K.M.  Chem. A c t a  1973,  7,  J_;_ O r g a n o m e t . Chem. 1976,  (86) A c o m p l e x f o r m u l a t e d as ( 77 - C H )Cr (NO) B F „ has been isolated from the mixtures resulting after sequential t r e a t m e n t of aqueous s o l u t i o n s of ( 7 } - C H )Cr (NO) C 1 with AgN0 and N a B F „ [ 8 7 ] . T h i s compound i s b e t t e r f o r m u l a t e d a s [ ( r ? - C H )Cr (NO) O H ] B F „ . 5  5  5  2  5  5  5  2  3  5  5  5  2  (87) P i p e r , 2j_ 3 8 .  T.S.;  2  Wilkinson,  G.  J^_ I n o r g .  Nucl.  Chem.  1956,  (88) M a l i t o , J . T . P h . D . D i s s e r t a t i o n , U n i v e r s i t y of British C o l u m b i a , 1976. The c h a r a c t e r i s t i c spectral properties of t h i s c o m p l e x a r e a s f o l l o w s : I R ( C H C 1 ) *>(NO) 1846 ( s ) , 1742 ( v s ) c m " ; H NMR ( ( C D ) C O ) : 6 6.18 ( s , 5H, C H ) , 2.57 ( s , 3H, N C C H ) . 2  1  1  3  2  2  5  5  3  (89) See reference 85. It is tempting to formulate the organometallic product formed in this reaction as ( 7 } - C H )Fe (CO) B F „ . However, t h e IR d a t a r e p o r t e d f o r t h i s s p e c i e s (t>(CO) 2 0 5 0 , 2010 c m " ) do not agree with those d i s p l a y e d by a u t h e n t i c ( r j - C H )Fe (CO) B F „ (i/(CO) 2078, 2032 c m " ) r e c e n t l y i s o l a t e d by M a t t s o n and Graham [ 4 3 ] . 5  5  5  2  1  5  5  5  2  1  (90)  Legzdins,  (91) Hubbard, A r i z o n a , 1982.  P.;  Wassink, J . C ,  B.,  Ph.D.  submitted  for  Dissertation,  publication. University  of  103  APPENDIX  Selected Thesis  Infrared  Spectra  of  Compounds  Described  in  this  -C H )W(NO) C1 5  5  2  as  CH C1 2  2  solution o  ••••ox  ooo -oe  ooo -09 ooo -av 33NVJ._LIWSNVy_L%  QOO-os  oooo -o  Phenylethyne  as n e a t  liquid  109  3 , 3 , 4 , 4 - T e t r a m e t h y l - 1 - p h e n y l c y c l o b u t e n e as n e a t  liquid  I  n 4000  3600  3200  2800  2400  FREQUENCY (CM"') 2000 1800 1600  CD 1400  1200  1000  800  600  CO  121  (r? -C H -)Mo(NO) C 1 a s C H C 1 5  5  5  2  2  2  solution  122  1 23  (T7 -C H 5  5  5  )Cr(NO)2C1 as C H C 1 2  2  solution  u o  OO OOT -  OOO 'OS  OOO •OS OOO "Of 33NVI J. IWSNVM1Z  OOO "OS  oooo ••  [ ( r ? - C H )Cr(NO) 5  5  5  2  ]  2  as C H C 1 2  2  solution  

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