ISSN:
1432-2234
Keywords:
Pyramidality of carbanions
;
Competitive inductive and conjugative effects
;
Ab initio calculations on carbanions
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Abstract Ab initio SCF calculations using uniform quality extended basis set supplemented with polarization functions predict a slightly pyramidal carbanion centre in ⊖:CH2-C≡N. This finding is in contrast to the usual finding of planar geometry of carbanion centres generated next to other conjugative groups. Although the predicted barrier to pyramidal inversion is very small (∼0.1 kcal/mole) it is estimated that correlation energy contributions, neglected in any SCF calculations, may be too small to remove the barrier. The present results confirm earlier experimental findings that counter-ion and solvent effects can have a dominant role in determining the geometry of this unusual ion in actual chemical systems.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00550037
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