Mechanism of the photochemical dehydrogenation and transfer-dehydrogenation of alkanes catalyzed by trans-Rh(PMe3)2(CO)Cl

J. A. Maguire; W. T. Boese; M. E. Goldman; A. S. Goldman

doi:10.1016/0010-8545(90)80088-B

Mechanism of the photochemical dehydrogenation and transfer-dehydrogenation of alkanes catalyzed by trans-Rh(PMe₃)₂(CO)Cl

J. A. Maguire, W. T. Boese, M. E. Goldman, A. S. Goldman

Rutgers University

Research output: Contribution to journal › Article › peer-review

58 Citations (Scopus)

Abstract

Rh(PMe₃)₂(CO)Cl catalyzes the photochemical dehydrogenation of alkanes to yield alkenes. H₂ is evolved or, in the presence of potential hydrogen acceptors such as t-butylethylene and styrene, hydrogen can be transferred to the olefins. The photokinetics and selectivity of the dehydrogenation reactions have been investigated. Both reactions proceed via a single photochemical step, photoextrusion of carbon monoxide from Rh(PMe₃)₂(CO)Cl. Study of the transfer-dehydrogenation, particularly of the product ratio (H₂ : hydrogenated acceptor), reveals aspects of the dehydrogenation mechanism including steps subsequent to the turnover-limiting step.

Original language	English
Pages (from-to)	179-192
Number of pages	14
Journal	Coordination Chemistry Reviews
Volume	97
Issue number	C
DOIs	https://doi.org/10.1016/0010-8545(90)80088-B
Publication status	Published - Jan 1990

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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title = "Mechanism of the photochemical dehydrogenation and transfer-dehydrogenation of alkanes catalyzed by trans-Rh(PMe3)2(CO)Cl",

abstract = "Rh(PMe3)2(CO)Cl catalyzes the photochemical dehydrogenation of alkanes to yield alkenes. H2 is evolved or, in the presence of potential hydrogen acceptors such as t-butylethylene and styrene, hydrogen can be transferred to the olefins. The photokinetics and selectivity of the dehydrogenation reactions have been investigated. Both reactions proceed via a single photochemical step, photoextrusion of carbon monoxide from Rh(PMe3)2(CO)Cl. Study of the transfer-dehydrogenation, particularly of the product ratio (H2 : hydrogenated acceptor), reveals aspects of the dehydrogenation mechanism including steps subsequent to the turnover-limiting step.",

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T1 - Mechanism of the photochemical dehydrogenation and transfer-dehydrogenation of alkanes catalyzed by trans-Rh(PMe3)2(CO)Cl

AU - Maguire, J. A.

AU - Boese, W. T.

AU - Goldman, M. E.

AU - Goldman, A. S.

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N2 - Rh(PMe3)2(CO)Cl catalyzes the photochemical dehydrogenation of alkanes to yield alkenes. H2 is evolved or, in the presence of potential hydrogen acceptors such as t-butylethylene and styrene, hydrogen can be transferred to the olefins. The photokinetics and selectivity of the dehydrogenation reactions have been investigated. Both reactions proceed via a single photochemical step, photoextrusion of carbon monoxide from Rh(PMe3)2(CO)Cl. Study of the transfer-dehydrogenation, particularly of the product ratio (H2 : hydrogenated acceptor), reveals aspects of the dehydrogenation mechanism including steps subsequent to the turnover-limiting step.

AB - Rh(PMe3)2(CO)Cl catalyzes the photochemical dehydrogenation of alkanes to yield alkenes. H2 is evolved or, in the presence of potential hydrogen acceptors such as t-butylethylene and styrene, hydrogen can be transferred to the olefins. The photokinetics and selectivity of the dehydrogenation reactions have been investigated. Both reactions proceed via a single photochemical step, photoextrusion of carbon monoxide from Rh(PMe3)2(CO)Cl. Study of the transfer-dehydrogenation, particularly of the product ratio (H2 : hydrogenated acceptor), reveals aspects of the dehydrogenation mechanism including steps subsequent to the turnover-limiting step.

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