Oxidative Addition of Haloalkanes to Metal Centers: A Mechanistic Investigation
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Photolysis of CpRe(CO)3 in the presence of dichloromethane results in the initial formation of the CpRe(CO)2(ClCH2Cl) complex followed by insertion of the metal into the C-Cl bond. The activation enthalpy is determined to be 20.4 kcal/mol, and with the assistance of DFT calculations, a radical mechanism is proposed for the oxidative addition reaction. Photolysis of Ni(CO)2(PPh3)2 with dihalomethanes also results in oxidative addition, but the intermediacy of a halogen-bound adduct has not been established. © 2014 American Chemical Society.
author list (cited authors)
Yempally, V., Moncho, S., Muhammad, S., Brothers, E. N., Arndtsen, B. A., & Bengali, A. A.