Oxidative Addition of Haloalkanes to Metal Centers: A Mechanistic Investigation
dataset
posted on 2014-07-14, 00:00 authored by Veeranna Yempally, Salvador Moncho, Sohail Muhammad, Edward N. Brothers, Bruce A. Arndtsen, Ashfaq A. BengaliPhotolysis
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.
