Oxidation of η6-arene Complexes of Group VI Metals. Part 3. Di-iodide Catalyzed Carbonylation of Molybdenum(0)- η6-arene Complexes to Mo(CO)6 and Experimental Evidence of an Inner-sphere Electron Transfer Reaction Between Centers of Molybdenum(II) and Molybdenum(0) - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Gazzetta Chimica Italiana Année : 1988

Oxidation of η6-arene Complexes of Group VI Metals. Part 3. Di-iodide Catalyzed Carbonylation of Molybdenum(0)- η6-arene Complexes to Mo(CO)6 and Experimental Evidence of an Inner-sphere Electron Transfer Reaction Between Centers of Molybdenum(II) and Molybdenum(0)

Résumé

Carbonylation of Mo(CO)3(η6-arene) has been found to be catalysed by I2, or by [MoI(CO)3(η6-arene)][Mo2I5(CO)6] or by Mo2I4(CO)8. Earlier papers in this series have shown the latter molybdenum(II) complexes to be the products of Mo(CO)3(η6-arene) oxidation by I2 in the absence or in the presence of carbon monoxide, respectively. The rate of carbonylation to Mo(CO)6 decreases with the methyl substitution on the carbocyclic ligand. A fast process between Mo(CO)3(η6-arene) and [MoI(CO)3(η6-arene')]X (X = BPh4, [Mo2I5(CO)6]) leading to Mo(CO)3(η6-arene') and [MoI(CO)3(η6-arene)]X has been observed in dichloromethane solution. This is believed to be in fact an inner-sphere iodide transfer process, i.e. an Mo(0)-Mo(II) two-electron transfer simulating an arene exchange. The [MoI(CO)3(η6-arene)]+ cation is believed to play an important role in both the apparent arene exchange and the carbonylation process via an iodide-bridged mixed-valence common intermediate.
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hal-03574282 , version 1 (15-02-2022)

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Aldo Barbati, Fausto Calderazzo, Rinaldo Poli. Oxidation of η6-arene Complexes of Group VI Metals. Part 3. Di-iodide Catalyzed Carbonylation of Molybdenum(0)- η6-arene Complexes to Mo(CO)6 and Experimental Evidence of an Inner-sphere Electron Transfer Reaction Between Centers of Molybdenum(II) and Molybdenum(0). Gazzetta Chimica Italiana, 1988, 118, pp.589-594. ⟨hal-03574282⟩
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