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Substitution and Isomerization of Asymmetric β-Diketonato Rhodium(I) Complexes: A Crystallographic and Computational Study

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journal contribution
posted on 14.06.2010, 00:00 authored by Kathrin H. Hopmann, Nomampondomise F. Stuurman, Alfred Muller, Jeanet Conradie
Ligand substitution of PPh3 for CO in the asymmetric square-planar β-diketonato complex [Rh(PhCOCHCOCH2CH3)(CO)2] leads to formation of the monosubstituted [Rh(PhCOCHCOCH2CH3)(CO)(PPh3)] product. Two geometrical product isomers are possible, which unexpectedly crystallize in the same crystal lattice. DFT calculations of the substitution reaction support a two-step mechanism, involving temporary dissociation of a β-diketonato ligand and formation of a square-planar intermediate. Analysis of the mechanisms involved in product isomerization suggests several noncatalyzed and solvent-assisted interconversion pathways.