| DFT Investigation on the Insertion Reaction of an Isocyanide into the（Silyl）（silylene）molybdenum Si-C Bond |
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| 作者姓名： | ZHAO Yan-Yun CHENG Xue-Li LI Li-Qing LI Zhen |
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| 作者单位： | Department School of Chemistry and Chemica Engineering Environmental Sciences,Taishan University;Scientific Research Department,Taishan University |
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| 基金项目： | supported by the National Natural Science Foundation of China (No.11174215) |
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| 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 functions22] 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.
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| 关 键 词： | 插入反应 密度泛函理论 硅烯 过渡金属配合物 异氰酸 有机金属化学 硅基 评估标准 |
DFT Investigation on the Insertion Reaction of an Isocyanide into the(Silyl)(silylene)molybdenum Si-C Bond |
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| ZHAO Yan-Yun,CHENG Xue-Li,LI Li-Qing,LI Zhen.DFT Investigation on the Insertion Reaction of an Isocyanide into the(Silyl)(silylene)molybdenum Si-C Bond[J].Chinese Journal of Structural Chemistry,2012,31(4):473-478. |
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| Authors: | ZHAO Yan-Yuna CHENG Xue-Lia② LI Li-Qingb LI Zhen |
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| Institution: | 1. School of Chemistry and Chemica Engineering,Taishan University, Taian, Shandong 271021, China
2. Scientific Research Department, Taishan University, Taian, Shandong 271021, China |
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| Abstract: | 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 functions22] 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. |
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| Keywords: | (silyl)(silylene)molybdenum isocyanide insertion DFT electronic population PCM |
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