The chemistry of silylene-transition-metal complexes LnM（=SiR2）SiR3 is one of the attractive synthetic targets in organometallic chemistry for such complexes are key intermediates in many transition metal-catalyzed ...The chemistry of silylene-transition-metal complexes LnM（=SiR2）SiR3 is one of the attractive synthetic targets in organometallic chemistry for such complexes are key intermediates in many transition metal-catalyzed systems.In the present work,the novel insertion reactions of an isocyanide into the Cp＊Mo（CO）2（=SiMe2）（SiMe3） Si-C bond were investigated extensively by using the DFT method.The effective core potentials（ECP） with a double-ζ valence basis set（LanL2DZ） were employed for Mo and Si and the standard 6-31G basis set for all other atoms.Polarization functions[22] were added for Si（ζd = 0.262）,C（ζd = 0.8） and N（ζd = 0.8）.The effect of solvent was evaluated with the standard PCM model.Our calculations show that the two-step channel is energetically favorable,and the solvation mode has minor influence on the relative energies.展开更多
基金supported by the National Natural Science Foundation of China (No.11174215)
文摘The chemistry of silylene-transition-metal complexes LnM（=SiR2）SiR3 is one of the attractive synthetic targets in organometallic chemistry for such complexes are key intermediates in many transition metal-catalyzed systems.In the present work,the novel insertion reactions of an isocyanide into the Cp＊Mo（CO）2（=SiMe2）（SiMe3） Si-C bond were investigated extensively by using the DFT method.The effective core potentials（ECP） with a double-ζ valence basis set（LanL2DZ） were employed for Mo and Si and the standard 6-31G basis set for all other atoms.Polarization functions[22] were added for Si（ζd = 0.262）,C（ζd = 0.8） and N（ζd = 0.8）.The effect of solvent was evaluated with the standard PCM model.Our calculations show that the two-step channel is energetically favorable,and the solvation mode has minor influence on the relative energies.
