113353-92-7Relevant academic research and scientific papers
An electron-transfer induced migratory insertion reaction originating from a 19-electron cobaltacyclic anion
Morneau, Andre,Donovan-Merkert, Bernadette T.,Geiger, William E.
, p. 96 - 101 (2000)
The cyclopentadienyl cobaltafluorenyl carbonyl complex Cp(CO)CoC12H8 (3) is reduced in THF in a one-electron irreversible process. The reduction products include the fluorenone radical anion, Fl-, which is proposed to arise through migratory insertion of the CO ligand into the metallacyclic Co-C bond of the 19-electron complex 3-. Electrochemical and IR analyses show that bulk electrolysis under N2 gives 1/3 equiv. each of Fl- and CpCo(CO)2 and 2/3 equiv. of a 17-electron anion [CpCoC12H8]- (2-) Under CO the yield of Fl- is quantitative. The insertion product is also formed when the reduction of the analogous phosphine complex Cp(PPh3)CoC12H8 is performed under CO. An equilibrium between 17- and 19-electron compounds is postulated to account for the synthetic and voltammetric observations. When the cobaltacycle Cp(PPh3)CoC4Ph4 (5) is reduced under carbon monoxide, the CO-insertion product is the π-cyclopentadienone complex CpCo(η4-C4Ph4O) (8). (C) 2000 Elsevier Science S.A.
