Oxidative Addition of Haloalkanes to Metal Centers: A Mechanistic Investigation
Organometallics, 2014•ACS Publications
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.
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.
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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