32356-70-0Relevant articles and documents
ELECTROCHEMISTRY OF COORDINATION COMPOUNDS. XX. ELECTROGENERATED Rh(CO)(PPh3)3 AND Ir(CO)(PPh3)3
Zotti, Gianni,Zecchin, Sandro,Pilloni, Giuseppe
, p. 61 - 72 (1983)
The redox behaviour of the d8 complexes + (M=Rh, Ir) was studied on platinum electrode in 1,2-dimethoxyethane by cyclic voltammetry, differential pulse voltammetry, and potentiostatic coulometry.The complexes show two reversible one-electron reductions consistent with the formation of the rare zerovalent M(CO)(PPh3)3 and the anionic - derivatives, respectively.The reduced species were characterized by ESR and IR spectroscopy.A significant feature is that the one-electron reduced intermediates, in spite of their radical nature, react very easily with molecules capable of reacting as proton rather than H-atom sources to give the hydride species HM(CO)(PPh3)3.A tentative interpretation of this behaviour is suggested.
Carbonylation of metal-oxygen bonds. Formation of carbalkoxydicarbonylbis(triphenylphosphine)iridium, ROC(O)Ir(CO)2(PPh3)2, by carbonylation of trans-alkoxycarbonylbis(triphenylphosphine)iridium, trans-ROIr(CO)(PPh3)2 (R = Me, n-Pr, Ph)
Rees, Wayne M.,Atwood, Jim D.
, p. 402 - 404 (2008/10/08)
Carbonylation of the complexes trans-MeOIr(CO)(PPh3)2, trans-(n-PrO)Ir(CO)(PPh3)2, and trans-PhOIr(CO)(PPh3)2 leads to carboalkoxy complexes ROC-(O)Ir(CO)2(PPh3)2 in high yield. Identification of the intermediate Ir(CO)3(PPh3)2+ OR- indicates a two-step mechanism - first displacement of the alkoxide from the coordination sphere and then nucleophilic attack on a carbon of the cationic carbonyl complex. The hydroxy complex did not undergo carbonylation under similar conditions.