Prediction of an inverse heavy-atom effect in H-C-CH(2)Br bromine substituent as a pi acceptor
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Journal of the American Chemical Society.
2002 May 22 ;
124 (20) :
5606-7.
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 pi-electron acceptor and overwhelming the even weaker effect of the pi-symmetry lone pair donor 4p orbital, which in itself would cause a small normal heavy-atom effect.
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