Oxidative addition of haloalkanes to metal centers: a mechanistic investigation

Yempally, V, Moncho, S, Sohail, M ORCID: https://orcid.org/0000-0002-8221-818X, Brothers, EN, Arndtsen, BA and Bengali, AA (2014) Oxidative addition of haloalkanes to metal centers: a mechanistic investigation. Organometallics, 33 (13). pp. 3591-3595. ISSN 0276-7333

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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.