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Hypervalent versus Nonhypervalent Carbon in Noble‐Gas Complexes
Author(s) -
Pierrefixe Simon C. A. H.,
Poater Jordi,
Im Chan,
Bickelhaupt F. Matthias
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200800013
Subject(s) - hypervalent molecule , isostructural , chemistry , neon , silicon , carbon fibers , noble gas , delocalized electron , atom (system on chip) , helium , crystallography , atomic physics , physics , materials science , organic chemistry , crystal structure , argon , reagent , composite number , computer science , embedded system , composite material
Silicon in [ClSiH 3 Cl] − is hypervalent, whereas carbon in [ClCH 3 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 [NgCH 3 Ng] + (Ng=He and Ne), which feature a delocalized D 3 h ‐symmetric structure with two equivalent CNg bonds? From Ng=Ar onwards, the [NgCH 3 Ng] + complex again acquires a propensity to localize one of its axial CNg bonds and to largely break the other one, and this propensity increases in the order Ng=Ar