Stereochemistry of the reaction products of the oxidative addition reaction of methyl iodide to [Rh((C4H3S)COCHCOR)(CO)(PPh3)]: A NMR and computational study. R = CF3, C6H5, C4H3S

A NMR study of the reaction mixture of the square planar [Rh((C4H3S)COCHCOR)(CO)(PPh3)] complex and CH3I, where R = CF3, C6H5 or C4H3S, revealed that two types of alkyl and one (R = CF3) or two (R = C6H5 or C4H3S) types of acyl species exist in the system. Two isomers of each species with an unsymmetrical β-diketonato ligand were observed. 1H–1H NOESY NMR unambiguously showed that the PPh3 group is in the apical position in the more stable RhIII-alkyl product. Theoretical computations of the equilibrium geometry of the possible reaction products, consistent with experimental observations, revealed that the first alkyl product results from trans addition to RhI and that the second thermodynamic alkyl product adopts an octahedral geometry with the PPh3 group and the iodide above and below the square planar plane. Theoretical computations also revealed that the thermodynamic acyl product adopts a square-pyramidal geometry with the COCH3 group in the apical position.