The mechanism of Rh（Ⅱ） carbene S-H insertion into H2S in gas phase has been studied by B3LYP functional. Calculation results showed that the Rh（Ⅱ） carbene S-H insertion into H2S took only stepwise channels and n...The mechanism of Rh（Ⅱ） carbene S-H insertion into H2S in gas phase has been studied by B3LYP functional. Calculation results showed that the Rh（Ⅱ） carbene S-H insertion into H2S took only stepwise channels and no concerted channels had been located, which was different from the Rh（Ⅱ） carbene C-H and O-H insertions.展开更多
The mechanisms of insertion of O-H bond of Rh（ Ⅱ ）-methylene carbene into methanol and ethanol were studied by using B3LYP functional both in gas phase and in CH2 C12. The formation of free alcoholic oxonium ylides...The mechanisms of insertion of O-H bond of Rh（ Ⅱ ）-methylene carbene into methanol and ethanol were studied by using B3LYP functional both in gas phase and in CH2 C12. The formation of free alcoholic oxonium ylides is found to be impossible. Alcoholic oxonium ylide are formed as the intermediates before beth the stepwise and the concerted transition states of insertion of O-H bend of Rh（ Ⅱ ）-methylene carbene into methanol and ethanol. With re- gard to the mechanisms of insertion of O-H of Rh（ Ⅱ ） -methylene carbene into alcohols, analysis of the energy bartiers of the two mechanisms indicate that the stepwise mechanism is more plausible than the concerted mechanism.展开更多
文摘The mechanism of Rh（Ⅱ） carbene S-H insertion into H2S in gas phase has been studied by B3LYP functional. Calculation results showed that the Rh（Ⅱ） carbene S-H insertion into H2S took only stepwise channels and no concerted channels had been located, which was different from the Rh（Ⅱ） carbene C-H and O-H insertions.
文摘The mechanisms of insertion of O-H bond of Rh（ Ⅱ ）-methylene carbene into methanol and ethanol were studied by using B3LYP functional both in gas phase and in CH2 C12. The formation of free alcoholic oxonium ylides is found to be impossible. Alcoholic oxonium ylide are formed as the intermediates before beth the stepwise and the concerted transition states of insertion of O-H bend of Rh（ Ⅱ ）-methylene carbene into methanol and ethanol. With re- gard to the mechanisms of insertion of O-H of Rh（ Ⅱ ） -methylene carbene into alcohols, analysis of the energy bartiers of the two mechanisms indicate that the stepwise mechanism is more plausible than the concerted mechanism.
