Disproportionation of RhII(cod) to RhI(cod) and RhIII(cycloocta-2,5-dien-1-yl):  Hydrogen Atom Transfer vs Electron and Proton Transfer

• Published in: Organometallics Vol. 22; no. 15; pp. 3022 - 3024
• Main Authors: Hetterscheid, Dennis G. H, de Bruin, Bas, Smits, Jan M. M, Gal, Anton W
• Format: Journal Article
• Language: English
• Published: American Chemical Society 21-07-2003
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om030192h

One-electron oxidation of [(dpa)RhI(cod)]+ yields [(dpa)RhII(cod)]2+, which reversibly binds dioxygen. In solution [(dpa)RhII(cod)]2+ disproportionates to [(Hdpa)RhI(cod)]2+ and two isomers of [(dpa)RhIII(cyclooctadienyl)]2+. This reaction proceeds most likely via abstraction of an allylic hydrogen atom by the RhII metallo radical.