Oxidative Addition of Haloalkanes to Metal Centers:
A Mechanistic Investigation
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Abstract
Photolysis
of CpRe(CO)<sub>3</sub> in the presence of dichloromethane
results in the initial formation of the CpRe(CO)<sub>2</sub>(ClCH<sub>2</sub>Cl) 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)<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub> with dihalomethanes also results in
oxidative addition, but the intermediacy of a halogen-bound adduct
has not been established
