Bystander effects on carbene rearrangements: A computational study

被引：18

作者：

Hill, BT ^{[1
]}

Zhu, ZD ^{[1
]}

Boeder, A ^{[1
]}

Hadad, CM ^{[1
]}

Platz, MS ^{[1
]}

机构：

[1] Ohio State Univ, Dept Chem, Columbus, OH 43210 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2002年 / 106卷 / 19期

关键词：

D O I：

10.1021/jp020108w

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Methylcarbene, dimethylcarbene, chloromethylcarbene, and tert-butylmethylcarbene were studied at the HF/6-31G*, MP2/6-31G*, B3LYP/6-31G*, MP2/6-31+G(2d,p), QCISD(T)/6-31G*//MP2/6-31G*, and QCISD-(T)/6-31+G(2d,p) levels. Minimum energy geometries of the singlet and triplet states of the carbenes were calculated. The barriers to 1,2-hydrogen migration for CH3C-X-->CH2=CHX were calculated and found to increase for X = Cl > CH3 > C(CH3)(3) > H. Isodesmic calculations indicate that the effect of the bystander group is to stabilize differentially the carbene reactant, thereby increasing the barrier to rearrangement for X = Cl > CH3 > C(CH3)(3) > H.

引用

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页码：4970 / 4979

页数：10

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