THEORETICAL STUDIES ON CARBENES AND CARBENOIDS （Ⅳ） ——ISOMERIZATIONS AND DECOMPOSITIONS OF CARBENOIDS H₂C=CLiCl AND H₂CLiCl

【摘要】 <正> The isomerizations and decompositions of carbenoids H₂C=CLiCl and H₂CLiCl have been studied by use of HF/STO-3G gradient method. Three equilibrium structures of H₂C=CLiCl were obtained, in which the linear structure has the lowest energy and the askew substituted structure was the next. It is found that the decomposition of H₂C=CLiCl undergoes a concerted FBW rearrangement and the inversion barrier of its askew substituted structure is 36 kJ/mol. For H₂CLiCl, the askew substituted structure, extending all valences of the carbon into a single hemisphere, is the lowest energy and its inversion barrier is 87 kJ/mol. The discussions on the factors concerned with the structural stabilities are given in this paper.更多还原

【Abstract】 The isomerizations and decompositions of carbenoids H₂C=CLiCl and H₂CLiCl have been studied by use of HF/STO-3G gradient method. Three equilibrium structures of H₂C=CLiCl were obtained, in which the linear structure has the lowest energy and the askew substituted structure was the next. It is found that the decomposition of H₂C=CLiCl undergoes a concerted FBW rearrangement and the inversion barrier of its askew substituted structure is 36 kJ/mol. For H₂CLiCl, the askew substituted structure, extending all valences of the carbon into a single hemisphere, is the lowest energy and its inversion barrier is 87 kJ/mol. The discussions on the factors concerned with the structural stabilities are given in this paper.更多还原