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Rhodium-Catalyzed C-C Coupling Reactions: Mechanistic Considerations


Hawkes, KJ and Cavell, KJ and Yates, BF, Rhodium-Catalyzed C-C Coupling Reactions: Mechanistic Considerations, Organometallics, 27, (18) pp. 4758-4771. ISSN 0276-7333 (2008) [Refereed Article]

DOI: doi:10.1021/om800472v


An alternative mechanism for intramolecular C-C coupling between heterocycles and alkenes with rhodium phosphine catalysts is presented involving oxidative addition, alkene insertion, and reductive elimination (route 2), as described previously for similar group 10 reactions by Cavell and McGuinness. Computational studies indicate that the rate-determining step is associated with reductive elimination of the product and overall barriers indicate this mechanism would be competitive with an alternative involving formation of a carbene complex derived from mechanistic work by Bergman, Ellman, and associates (route 1). Activation of the reacting azole through inclusion of an acid catalyst appears to support the route 2 mechanism. A much lower activation barrier is observed under acidic conditions, a result consistent with that found under experimental conditions. © 2008 American Chemical Society.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Transition metal chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Hawkes, KJ (Dr Kirsty Hawkes)
UTAS Author:Cavell, KJ (Professor Kingsley Cavell)
UTAS Author:Yates, BF (Professor Brian Yates)
ID Code:55270
Year Published:2008
Web of Science® Times Cited:37
Deposited By:Chemistry
Deposited On:2009-03-08
Last Modified:2015-01-21

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