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C-C sigma complexes of rhodium.

ABSTRACT: In this article, the complexes [Rh(Binor-S')(PR3)][BAr(4)(F)] (R = (i)Pr, Cy, C(5)H(9)) are described. A combination of x-ray crystallography, NMR spectroscopy, density functional theory, and "atoms in molecules" calculations unequivocally demonstrates that the complexes contain rare examples of metal...C-C agostic interactions. Moreover, they are fluxional on the NMR time scale, undergoing rapid and reversible C-C activation. Kinetic data and calculations point to a bismetallacyclobutane, Rh(V), intermediate.

SUBMITTER: Brayshaw SK

PROVIDER: S-EPMC1855424 | biostudies-literature | 2007 Apr

REPOSITORIES: biostudies-literature

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C-C sigma complexes of rhodium.

Brayshaw Simon K SK Sceats Emma L EL Green Jennifer C JC Weller Andrew S AS

Proceedings of the National Academy of Sciences of the United States of America 20070413 17

In this article, the complexes [Rh(Binor-S')(PR3)][BAr(4)(F)] (R = (i)Pr, Cy, C(5)H(9)) are described. A combination of x-ray crystallography, NMR spectroscopy, density functional theory, and "atoms in molecules" calculations unequivocally demonstrates that the complexes contain rare examples of metal...C-C agostic interactions. Moreover, they are fluxional on the NMR time scale, undergoing rapid and reversible C-C activation. Kinetic data and calculations point to a bismetallacyclobutane, Rh(V) ...[more]

PMID: 17435164

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