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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 CH 3 C X → CH 2 CHX were calculated and found to increase for X = Cl > CH 3 > C(CH 3 ) 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 > CH 3 > C(CH 3 ) 3 > H.
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Hill et al. (2002) studied this question.
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