Prediction of an Inverse Heavy-Atom Effect in H-C-CH2Br: Bromine Substituent as a Acceptor
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- 作者：Zdenek Havlas and Josef Michl
- 刊名：Journal of the American Chemical Society
- 出版年：2002
- 出版时间：May 22, 2002
- 年：2002
- 卷：124
- 期：20
- 页码：5606 - 5607
- 全文大小：76K
- 年卷期：v.124,no.20(May 22, 2002)
- ISSN：1520-5126
文摘
A comparison of spin-orbit coupling calculated [CASSCF(6,6)/(cc-pVDZ on C,H and VDZ+P on Br] for bromomethylcarbene and methylcarbene predicts a highly unusual inverse heavy-atom effect by the Br substituent, particularly at geometries near the syn conformation. This behavior is due to a vacant 4d orbital on the Br atom acting as a weak 
-electron acceptor and overwhelming the even weaker effect of the -symmetry lone pair donor 4p orbital, which in itself would cause a small normal heavy-atom effect.
-electron acceptor and overwhelming the even weaker effect of the -symmetry lone pair donor 4p orbital, which in itself would cause a small normal heavy-atom effect.