In the presence of Rh（COD）（dppe）Cl （COD=1, 5-cyclootadiene, dppe=1,2-bis-（diphenylphosphino）ethane） and CO, we studied the H/Cl exchange reaction between CH<sub>4</sub> and o-dichlorobenzene, and o...In the presence of Rh（COD）（dppe）Cl （COD=1, 5-cyclootadiene, dppe=1,2-bis-（diphenylphosphino）ethane） and CO, we studied the H/Cl exchange reaction between CH<sub>4</sub> and o-dichlorobenzene, and observed that the active species of the reaction is a complex containing dppe and carbonyl ligands. We suggest that the mechanism of exchange reaction may be described by the elementary reaction of oxidative addition and reductive elimination. In the presence of trans-PtHL<sub>2</sub>X （L=PEt<sub>3</sub>, P（n-Pr）<sub>3</sub>, P（n-Bu）<sub>3</sub>, PPh<sub>3</sub>; X=Cl<sup>-</sup>, Br<sup>-</sup>, I<sup>-</sup>, CN<sup>-</sup>） complexes, we have studied the oxidative chlorination reaction of methane. The catalytic activity was found to be related to the electron-donating properties and the cone angle of tertiary phosphine, as well as the trans-effect of X anionic ligands. In addition to the above reactions, we have also studied the insertion reaction of acetylene into C-H bond of methane catalyzed by organotransition-metal complexes containing heterocyclic chelate ligands, such as bipy, phen and TMEDA, in展开更多
基金This work was supported by the Natural Science Foundation of China
文摘In the presence of Rh（COD）（dppe）Cl （COD=1, 5-cyclootadiene, dppe=1,2-bis-（diphenylphosphino）ethane） and CO, we studied the H/Cl exchange reaction between CH<sub>4</sub> and o-dichlorobenzene, and observed that the active species of the reaction is a complex containing dppe and carbonyl ligands. We suggest that the mechanism of exchange reaction may be described by the elementary reaction of oxidative addition and reductive elimination. In the presence of trans-PtHL<sub>2</sub>X （L=PEt<sub>3</sub>, P（n-Pr）<sub>3</sub>, P（n-Bu）<sub>3</sub>, PPh<sub>3</sub>; X=Cl<sup>-</sup>, Br<sup>-</sup>, I<sup>-</sup>, CN<sup>-</sup>） complexes, we have studied the oxidative chlorination reaction of methane. The catalytic activity was found to be related to the electron-donating properties and the cone angle of tertiary phosphine, as well as the trans-effect of X anionic ligands. In addition to the above reactions, we have also studied the insertion reaction of acetylene into C-H bond of methane catalyzed by organotransition-metal complexes containing heterocyclic chelate ligands, such as bipy, phen and TMEDA, in
