American Chemical Society
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Influence of the Nature of the Ligand on Dirhodium(II) Carbene Species: A Theoretical Analysis

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journal contribution
posted on 2008-06-23, 00:00 authored by Julio Lloret, Jorge J. Carbó, Carles Bo, Agustí Lledós, Julia Pérez-Prieto
The influence of three prototypic families of bridging ligands (carboxylate, carboxamidate, and ortho-metalated arylphosphines) on the electronic structure of dirhodium(II) carbene complexes was theoretically analyzed. The calculations indicated that the electron donation of the ligand to the Rh atom, rather than the chelating ability or the metal−ligand orbital mixing, was responsible for tuning carbene charge via back-donation, which can influence the reactivity and selectivity of the dirhodium complexes in catalytic carbene transfer reactions.