Oxidative Addition of Haloalkanes to Metal Centers: A Mechanistic Investigation
Organometallics2014Vol. 33(13), pp. 3591–3595
Citations Over TimeTop 23% of 2014 papers
Veeranna Yempally, Salvador Moncho, Muhammad Sohail, Edward N. Brothers, Bruce A. Arndtsen, Ashfaq A. Bengali
Abstract
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.
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