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Metal–metal multiple bonded intermediates in catalysis

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Abstract

Metal–metal bonded Rh2 and Ru2 complexes having a paddlewheel-type structure are exceptional catalysts for a broad range of organic transformations. I review here the recent efforts towards the observation and characterization of intermediates in these reactions that have previously eluded detection. Specifically, mechanistic investigations of carbenoid and nitrenoid reactions of Rh2(II,II)-tetracarboxylate compounds have led to the observation of a metastable Rh2(II,II) carbene complex as well as a mixed-valent Rh2(II,III)-amido intermediate. Related Ru2 nitrido compounds have been studied and found to undergo intramolecular C–H amination reactions as well as intermolecular reaction with triphenylphosphine.

Compounds with a linear M–M=G structure, with M = Rh or Ru and G = carbene, nitrene, or nitride groups, are described as important reactive intermediates in catalysis.

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Acknowledgements

I thank the US Department of Energy and the National Science Foundation for supporting my research under the following grants: DE-FG02-10ER16204, CHE-1205646, and CHE-1300464.

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  1. Department of Chemistry, University of Wisconsin – Madison, 1101 University Ave., Madison, WI, 53706, USA

    JOHN F BERRY

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BERRY, J.F. Metal–metal multiple bonded intermediates in catalysis. J Chem Sci 127, 209–214 (2015). https://doi.org/10.1007/s12039-015-0773-6

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