South African Journal of Chemistry
On-line version ISSN 1996-840X
CONRADIE, Marrigje M. and CONRADIE, Jeanet. Methyl iodide oxidative addition to rhodium(I) complexes: A DFT and NMR study of [Rh(FcCOCHCOCf3)(CO)(pph3)] and the rhodium(III) reaction products. S.Afr.j.chem. (Online) [online]. 2008, vol.61, pp. 102-111. ISSN 1996-840X.
A theoretical (DFT) study of the equilibrium geometry of the possible reaction products of the oxidative addition reaction [Rh(FcCOCHCOCF3)(CO)(PPh3)] + CH3I (Fc = ferrocenyl), consistent with experimental observations, revealed that the first alkyl product results from trans addition to RhI. Isomerization via an acyl intermediate leads to a second octahedral alkyl product with the PPh3 group and the iodide above and below the square plane. Theoretical computations also revealed that the thermodynamic acyl product adopts a square-pyramidal geometry with the COCH3 group in the apical position.
Keywords : DFT; computational; rhodium; B-diketone, NMR.