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. 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 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 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.