Hypervalent versus Nonhypervalent Carbon in Noble-Gas Complexes

Silicon in [ClSiH3Cl]− is hypervalent, whereas carbon in [ClCH3Cl]− is not. We have recently shown how this can be understood in terms of the ball‐in‐a‐box model, according to which silicon fits perfectly into the box that is constituted by the five substituents, whereas carbon is too small and,...

Full description

Saved in:
Bibliographic Details
Published in:Chemistry : a European journal 2008-08, Vol.14 (23), p.6901-6911
Main Authors: Pierrefixe, Simon C. A. H., Poater, Jordi, Im, Chan, Bickelhaupt, F. Matthias
Format: Article
Language:English
Subjects:
bond theory
carbon
density functional calculations
hypervalent compounds
noble gases
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Silicon in [ClSiH3Cl]− is hypervalent, whereas carbon in [ClCH3Cl]− is not. We have recently shown how this can be understood in terms of the ball‐in‐a‐box model, according to which silicon fits perfectly into the box that is constituted by the five substituents, whereas carbon is too small and, in a sense, “drops to the bottom” of the box. But how does carbon acquire hypervalency in the isostructural and isoelectronic noble gas (Ng)/methyl cation complexes [NgCH3Ng]+ (Ng=He and Ne), which feature a delocalized D3h‐symmetric structure with two equivalent CNg bonds? From Ng=Ar onwards, the [NgCH3Ng]+ complex again acquires a propensity to localize one of its axial CNg bonds and to largely break the other one, and this propensity increases in the order Ng=Ar
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.200800013