- Library Home /
- Search Collections /
- Open Collections /
- Browse Collections /
- UBC Theses and Dissertations /
- Nitrosyl hydrides and cations of Group VI transition...
Open Collections
UBC Theses and Dissertations
UBC Theses and Dissertations
Nitrosyl hydrides and cations of Group VI transition metals Oxley, Jimmie Carol
Abstract
The novel bimetallic hydrides [(n⁵-C₅H₅)W(N0)IH]₂ and [(n⁵-C₅H₅)W(N0)H₂]₂ can be prepared sequentially by the metathesis of [(n⁵-C₅H₅)W(N0)IH₂]₂ with Na[H₂Al(0CH₂CH₂0CH₃)₂]. Analyses of the ¹H NMR spectra of C[(n⁵-C₅H₅)W(N0)IH]₂ and [(n⁵-C₅H₅)W(N0)IH₂]₂ show the former contains hydride ligands bound to tungsten in a terminal fashion, while the latter possesses two terminal and two bridging hydrides. Addition of a Lewis base to [(n⁵-C₅H₅)W(N0)IH]₂ results in the formation of hydride species (n⁵-C₅H₅)W(N0)IHL (L = P(0Ph)₃, P(0Me)₃, PPh₃); in like manner, the dimer [(n⁵-C₅H₅)W(N0)IH₂]₂ is cleaved by triphenylphosphite to form the monomer cis or trans [(n⁵-C₅H₅)W(N0)IH₂[P(0Ph)₃]. A comparison is made of the reactivity of the tungsten-hydrogen link in the nitrosyl hydrides (n⁵-C₅H₅)- W(N0)IH[P(0Ph)₃], (n⁵-C₅H₅)W(N0)₂H, and (n⁵-C₅H₅)W(N0)IH₂[P(0Ph)₃]. The Mo(N0)₂²⁺ unit is obtained as the tetrakis-solvate via chloride abstraction from Mo(N0)₂Cl₂ by AgBF₄ or nitrosylation of Mo(C0)₆ by NOPF₆ in coordinating solvents such as nitromethane, acetonitrile, or tetrahydro-furan. The unsolvated complex [Mo(N0)₂(PF₆)₂][aub=n] is produced if the latter reaction is performed in dichloromethane; however, it readily converts to [Mo(N0)₂S₄](PF₆)₂ upon exposure to coordinating solvents (S). Hard Lewis bases (L = CH₃CN , 0PPh₃ or L₂ = 2 ,2-bipyridine replace the solvent molecules in [Mo(N0)₂S₄]X₂ (X = BF₄⁻, PF₆⁻) forming complexes [Mo(N0)₂L₄]²⁺ or [Mo(N0)₂L₂S₂]²⁺ depending upon the solvent employed. Reagents capable of being oxidized appear to reduce the dinitrosyl dication without permanent coordination to the molybdenum centre. Reduction of [Mo(NO)₂S₄](PF₆)₂ or [Mo(N0)₂(PF₆)₂][sub=b] is effected by sodium amalgam (one equivalent); addition of a ligand L₂ (L₂ = 2,2-bipyridyl, 3,4,7,8-tetramethyl-1,1O-phenanthroline) to the reaction mixture permits the isolation of [M(NO)₂L₂]₂(PF₆)₂. Addition of excess ligand results in the formation of non-nitrosyl containing species [Mp(L₂)₃]PF₆ (L = 0PPh₃ or L₂ = 3,4,7,8-tetramethyl-1 ,10-phenanthro- line). Decomposition of the nitrosyl species results from attempts to reduce [Mo(NO)₂S₄]²⁺ by two electrons. New complexes are identified by the aid of IR and ¹H, ¹⁹F, or ³¹P NMR spectroscopy and conductance measurements. Attempts to prepare thionitrosyl analogues of [Mo(N0)₂L₄]²⁺ have met with limited success; the only wel1-characterized thionitrosyls isolated in this study are the known (n⁵-C₅H₅)Cr(C0)₂NS and the new [(n⁵-C₅H₅)Mo-(N0)(NS)PPh₃]BF₄. Also discussed is the interaction of NOPF₆ with solvents. NOPF₆ has been found to react slowly with acetonitrile, a common solvent for nitro-sonium salts.
Item Metadata
Title |
Nitrosyl hydrides and cations of Group VI transition metals
|
Creator | |
Publisher |
University of British Columbia
|
Date Issued |
1983
|
Description |
The novel bimetallic hydrides [(n⁵-C₅H₅)W(N0)IH]₂ and [(n⁵-C₅H₅)W(N0)H₂]₂ can be prepared sequentially by the metathesis of [(n⁵-C₅H₅)W(N0)IH₂]₂ with Na[H₂Al(0CH₂CH₂0CH₃)₂]. Analyses of the ¹H NMR spectra of
C[(n⁵-C₅H₅)W(N0)IH]₂ and [(n⁵-C₅H₅)W(N0)IH₂]₂ show the former contains
hydride ligands bound to tungsten in a terminal fashion, while the latter
possesses two terminal and two bridging hydrides. Addition of a Lewis base
to [(n⁵-C₅H₅)W(N0)IH]₂ results in the formation of hydride species
(n⁵-C₅H₅)W(N0)IHL (L = P(0Ph)₃, P(0Me)₃, PPh₃); in like manner, the dimer
[(n⁵-C₅H₅)W(N0)IH₂]₂ is cleaved by triphenylphosphite to form the monomer
cis or trans [(n⁵-C₅H₅)W(N0)IH₂[P(0Ph)₃]. A comparison is made of the
reactivity of the tungsten-hydrogen link in the nitrosyl hydrides (n⁵-C₅H₅)-
W(N0)IH[P(0Ph)₃], (n⁵-C₅H₅)W(N0)₂H, and (n⁵-C₅H₅)W(N0)IH₂[P(0Ph)₃].
The Mo(N0)₂²⁺ unit is obtained as the tetrakis-solvate via chloride abstraction from Mo(N0)₂Cl₂ by AgBF₄ or nitrosylation of Mo(C0)₆ by NOPF₆ in coordinating solvents such as nitromethane, acetonitrile, or tetrahydro-furan. The unsolvated complex [Mo(N0)₂(PF₆)₂][aub=n] is produced if the latter reaction is performed in dichloromethane; however, it readily converts to [Mo(N0)₂S₄](PF₆)₂ upon exposure to coordinating solvents (S). Hard Lewis bases (L = CH₃CN , 0PPh₃ or L₂ = 2 ,2-bipyridine replace the solvent molecules
in [Mo(N0)₂S₄]X₂ (X = BF₄⁻, PF₆⁻) forming complexes [Mo(N0)₂L₄]²⁺ or
[Mo(N0)₂L₂S₂]²⁺ depending upon the solvent employed. Reagents capable of being oxidized appear to reduce the dinitrosyl dication without permanent
coordination to the molybdenum centre. Reduction of [Mo(NO)₂S₄](PF₆)₂
or [Mo(N0)₂(PF₆)₂][sub=b] is effected by sodium amalgam (one equivalent); addition
of a ligand L₂ (L₂ = 2,2-bipyridyl, 3,4,7,8-tetramethyl-1,1O-phenanthroline)
to the reaction mixture permits the isolation of [M(NO)₂L₂]₂(PF₆)₂. Addition of excess ligand results in the formation of non-nitrosyl containing
species [Mp(L₂)₃]PF₆ (L = 0PPh₃ or L₂ = 3,4,7,8-tetramethyl-1 ,10-phenanthro-
line). Decomposition of the nitrosyl species results from attempts to
reduce [Mo(NO)₂S₄]²⁺ by two electrons. New complexes are identified by the aid of IR and ¹H, ¹⁹F, or ³¹P NMR spectroscopy and conductance measurements.
Attempts to prepare thionitrosyl analogues of [Mo(N0)₂L₄]²⁺ have met with limited success; the only wel1-characterized thionitrosyls isolated in this study are the known (n⁵-C₅H₅)Cr(C0)₂NS and the new [(n⁵-C₅H₅)Mo-(N0)(NS)PPh₃]BF₄.
Also discussed is the interaction of NOPF₆ with solvents. NOPF₆ has been found to react slowly with acetonitrile, a common solvent for nitro-sonium salts.
|
Genre | |
Type | |
Language |
eng
|
Date Available |
2010-05-02
|
Provider |
Vancouver : University of British Columbia Library
|
Rights |
For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use.
|
DOI |
10.14288/1.0060661
|
URI | |
Degree | |
Program | |
Affiliation | |
Degree Grantor |
University of British Columbia
|
Campus | |
Scholarly Level |
Graduate
|
Aggregated Source Repository |
DSpace
|
Item Media
Item Citations and Data
Rights
For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use.