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化学学报
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化学学报 ›› 1988, Vol. 46 ›› Issue (12): 1155-1160.    下一篇

研究论文

亚烷基卡宾XYC=C:(X,Y=C1, H, Me, F)的1,2-重排反应的从头算研究

王秉泽;邓从豪   

  1. 山东大学化学系
  • 发布日期:1988-12-15

Ab initio study of the 1,2-rearrangements of alkylidenecarbenes XYC=C:(X,Y=Cl, H, Me and F)

WANG BINGZE;DENG CONGHAO   

  • Published:1988-12-15

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本文用RHF/STO-3G解析梯度方法研究了亚烷基卡宾XYC=C:(X, Y=Cl, H, Me和F)的重排反应, 给出了平衡态与过渡态构型. 对该组体系的计算发现: 基团的迁移活性顺序为Cl>H>Me>F; 迁移性小的基团增大迁移基团的迁移活性; 取代基不同一般比取代基相同的卡宾稳定性低; 基团的迁移活性顺序与电负性顺序不一致; 中心原子与C=C双键夹角小的基团优先迁移.

关键词: 反应机理, 乙炔, 碳烯, 重排反应, 从头计算法, 过渡态理论, 势垒, 解析, 梯度算法

The 1,2-rearrangement of the title species was studied by the RHF/STO-3G gradient method. The equilibrium and transition structures are fully optimized. For these systems at the STO-3G level, the shift reactivities are in the order Cl > H > Me > F, which is different from that of their electronegativities. The fixed group with lower shift reactivity enhances that of the shift group. The carbenes with two identical substituents are generally more stable. The substituent with a smaller angle formed by its central atom with the C:C bond migrates first.

Key words: REACTION MECHANISM, ACETYLENE, CARBENE, REARRANGEMENT REACTION, AB INITIO CALCULATION, TRANSITION STATE THEORY, POTENTIAL BARRIER, ANALYTIC, GRADIENT ALGORITHM

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