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A combined experimental and computational study of fluxional processes in sigma amine-borane complexes of rhodium and iridium

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Author(s)

  • Andrés G. Algarra
  • Laura J. Sewell
  • Heather C. Johnson
  • Stuart A. Macgregor
  • Andrew S. Weller

Department/unit(s)

Publication details

JournalDalton Transactions
DatePublished - 7 Aug 2014
Issue number29
Volume43
Number of pages11
Pages (from-to)11118-11128
Original languageEnglish

Abstract

A combined experimental and computational study on the fluxional processes involving the M-H and B-H positions in the sigma amine-borane complexes [M(PR3)2(H)22-H 3B·NMe3)][BArF 4] (M = Rh, Ir; R = Cy for experiment; R = Me, Cy for computation; ArF = 3,5-(CF3)2C6H3) is reported. The processes studied are: B-H bridging/terminal exchange; reaction with exogenous D2 leading to exchange at M-H; and intramolecular M-H/B-H exchange. Experimentally it was found that B-H bridging/terminal exchange is most accessible and slightly favoured for Rh; D2/M-H exchange occurs at qualitatively similar rates for both M = Rh and Ir, while M-H/B-H exchange is the slowest overall, with the Ir congener having a lower barrier than Rh. Evidence for the isotopic perturbation of equilibrium is also reported for the BH/BD isotopologues of [Ir(PCy3)2(H)22-H3B·NMe3)][BArF 4]. DFT calculations using model complexes (R = Me) qualitatively reproduce the relative rates of the various exchange processes for both M = Rh and Ir, i.e. barriers for B-H bridging/terminal exchange are less than those for M-H/H2 exchange, which in turn are less than those for M-H/B-H exchange. Which metal promotes these processes more effectively depends upon the nature of the rate-limiting transition state, which can change between Rh and Ir. Computational analysis of the full experimental system (R = Cy) reveals similar overall trends in terms of the relative ease of the various exchange processes. However, there are differences in the details, and these are discussed. This journal is

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