Kinetic studies on catalytic properties of rhodium complexes in solution
department or school: Science, Faculty of
department or school: Chemistry, Department of
data provider: DSpace
degree campus: UBCV
creator: Rempel, Garry Llewellyn
issued: 2011-09-15T22:44:11Z
issued: 1968
related degree: Doctor of Philosophy - PhD
degree grantor: University of British Columbia
description: Kinetic studies of a number of interesting and significant reactions involving activation of molecular hydrogen, simple olefins and carbon monoxide by solutions of rhodium trichloride trihydrate are described. RhCl₃∙3H₂O in N,N-dimethylacetamide solution is an effective catalyst for the homogeneous hydrogenation of a variety of substituted ethylenes as well as for ethylene itself. The kinetics of the RhCl₃∙3H₂O catalyzed hydrogenation of maleic acid in dimethylacetamide media suggest a mechanism involving an initial hydrogen reduction of rhodium (III) to rhodium (I), which is stabilized in solution by rapid complexing with maleic acid. The rhodium (i) maleic acid complex undergoes a subsequent reaction with hydrogen to produce succinic acid and rhodium (l) again, via an intermediate containing both coordinated maleic acid and hydrogen. In aqueous acid-chloride solution, rhodium (I) olefin complexes also form, but no subsequent homogeneous hydrogenation is apparent. Solutions of RhCl₃∙3H₂O in dimethylacetamide react with ethylene to form a rhodium (I) ethylene complex. Examination of the kinetics of the reaction suggest that the reaction proceeds through an initial dissociation of a chloro rhodium (III) species. A resulting intermediate rhodium (III) ethylene complex is decomposed by water to rhodium (I) which is stabilized by rapid reaction with further ethylene as an olefin complex. The resulting rhodium (I) ethylene complex subsequently acts as a dimerization catalyst for the production of butenes. Ethylene catalyzes at ambient temperatures the production of the [Rh(H₂O)₄Cl₂ ]⁺ cation from aqueous solutions of RhCl₃∙3H₂O; at higher temperatures metallic rhodium is formed. Carbon monoxide reacts with chlororhodate (III) complexes in aqueous HCl solution to form the anionic species [Rh(I)(CO)₂Cl₂]⁻. The observed kinetics indicate that [Rh(I)(CO)₂Cl₂]⁻ is autocatalytically produced; the mechanism postulated involves initial production of some [Rh(I)(CO)₂Cl₂]⁻ through…
aggregated CHO: https://circle.library.ubc.ca/rest/handle/2429/37415
note: KINETIC STUDIES ON CATALYTIC PROPERTIES OF RHODIUM COMPLEXES IK SOLUTION by GARRY LLEWELLYN REMPEL B.Sc.(Hons.) The University of British Columbia, 1965 A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY ' in the Department of CHEMISTRY We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA Ap r i l , 1968 In p r e s e n t i n g t h i s t h e s i s i n p a r t i a l f u l f i l m e n t o f t h e r e q u i r e m e n t s f o r an a d v a n c e d d e g r e e a t t h e U n i v e r s i t y o f B r i t i s h C o l u m b i a , I a g r e e t h a t t h e L i b r a r y s h a l l m a k e i t f r e e l y a v a i l a b l e f o r r e f e r e n c e a n d s t u d y . I f u r t h e r a g r e e t h a t p e r m i s s i o n f o r e x t e n s i v e c o p y i n g o f t h i s t h e s i s f o r s c h o l a r l y p u r p o s e s may be g r a n t e d by t h e H e a d o f my D e p a r t m e n t o r by h i s r e p r e s e n -t a t i v e s . I t i s u n d e r s t o o d t h a t c o p y i n g o r p u b l i c a t i o n o f t h i s t h e s i s f o r f i n a n c i a l g a i n s h a l l n o t be a l l o w e d w i t h o u t my w r i t t e n p e r m i s s i o n . D e p a r t m e n t n f Chemistry The U n i v e r s i t y o f B r i t i s h C o l u m b i a V a n c o u v e r 8, C a n a d a D a t e 23rd A p r i l , 1968 ABSTRACT K inet ic studies of a number of i n te res t ing and s i g n i f i c a n t reac -t ions invo lv ing c . c t i vat ion of molecular hydrogen, simple o l e f i n s and carbon monoxide by solut ions of rhodium t r i c h l o r i d e t r ihydrate are descr ibed. RhCl^'SH^O i n N,N-dimethylacetamide so lut ion i s an e f fec t i ve cata lys t fo r the homogeneous hydrogenation of a var ie ty of subst i tuted ethylenes as w e l l as for ethylene i t s e l f . The k i n e t i c s of the RhCl^^H^O catalyzed hydrogenation of maleic ac id in dimethylacetamide media suggest a mechanism invo lv ing an i n …
has type: Thesis/Dissertation
is shown at: 10.14288/1.0062214
language: eng
degree discipline: Chemistry
provider: Vancouver : University of British Columbia Library
publisher: University of British Columbia
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.
scholar level: Graduate
type: Text
identifier URI: http://hdl.handle.net/2429/37415