122905-48-0Relevant academic research and scientific papers
OXIDATION OF η6-ARENE COMPLEXES OF GROUP VI METALS. III. DI-IODINE-CATALYSED CARBONYLATION OF MOLYBDENUM(0)-η6-ARENE COMPLEXES TO Mo(CO)6 AND EXPERIMENTAL EVIDENCE OF AN INNER-SPHERE ELECTRON-TRANSFER REACTION BETWEEN CENTRES OF MOLYBDENUM(II) AND MOLYBDENUM(0)
Barbati, Aldo,Calderazzo, Fausto,Poli, Rinaldo
, p. 589 - 594 (2007/10/02)
Carbonylation of Mo(CO)3(η6-arene) has been found to be catalysed by I2, or by 6-arene)> 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 6-arene')>X (X = BF4, ) leading to Mo(CO)3(η6-arene') and 6-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 6-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.
