Agostic versus Terminal Ethyl Rhodium Complexes: A Combined Experimental and Theoretical Study

作者:Geer Ana M; Lopez Jose A; Ciriano Miguel A; Tejel Cristina
来源:Organometallics, 2016, 35(5): 799-808.
DOI:10.1021/acs.organomet.6b00036

摘要

Ethylene insertion into RhH bonds in complexes bearing an anionic fac-triphosphane ligand gives hydrido complexes, beta-agostic species, or noninteracting ethyl derivatives depending on the reaction conditions. Several chemical equilibria between these species have been analyzed by NMR and DFT calculations, which revealed that they are mainly controlled by the entropy. Moreover, beta-agostic species were found to be lower in enthalpy than the corresponding hydrideethylene complexes, probably due to the steric pressure exerted by the bulky fac-triphosphane ligand.

  • 出版日期2016-3-14

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