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Ligand substitution of PPh 3 for CO in the asymmetric square-planar β-diketonato complex [Rh-(PhCOCHCOCH 2 CH 3 )(CO) 2 ] leads to formation of the monosubstituted [Rh(PhCOCHCOCH 2 -CH 3 )(CO)(PPh 3 )] product. Two geometrical product isomers are possible, which unexpectedly crystallize in the same crystal lattice. DFT calculations of the substitution reaction support a twostep 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.

The influence of a sterically large ligand (CH3COC(C10H21OC6H4COO)COCH3)−, substituted on complex [Rh(CH3COC(C10H21OC6H4COO)COCH3)(CO)(PPh3)], on the ease of rhodium oxidation, is described.

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