DFT Investigation on the Insertion Reaction of an Isocyanide into the(Silyl)(silylene)molybdenum Si-C Bond  

作　　者：赵燕云 程学礼 李丽清 李震 

机构地区：[1]Department School of Chemistry and Chemica Engineering Environmental Sciences,Taishan University [2]Scientific Research Department,Taishan University [3]不详

出　　处：《Chinese Journal of Structural Chemistry》2012年第4期473-478,共6页结构化学（英文）

基　　金：supported by the National Natural Science Foundation of China (No.11174215)

摘　　要：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 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.

关 键 词：（silyl）（silylene）molybdenum isocyanide insertion DFT electronic population PCM 

分 类 号：O627.41[理学—有机化学]