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Methyl substituent effects in [H(n)X...XH(n)](+) three-electron-bonded radical cations (X = F, O, N, Cl, S, P; n = 1 - 3). An ab initio theoretical study

Methyl substituent effects in [H(n)X...XH(n)](+) three-electron-bonded radical cations (X = F, O, N, Cl, S, P; n = 1 - 3). An ab initio theoretical study

Journal of the American Chemical Society 124(10): 2371-2378

The effects of methyl substitution on the geometries and bonding energies of a systematic series of three-electron-bonded radical cations of the type [H(n)X...XH(n)](+), covering all possible symmetrical three-electron bonds that may take place between atoms of the second and third rows of the periodic table, have been investigated at the level of Møller-Plesset perturbation theory. Methyl substitution leads to significant weakening and lengthening of the X...X bond when X is a second-row atom. The effects increase with the number of substitutions and are more and more important in the series X = N, O, F. By contrast, methyl substitution leaves the bonding energies between third-row atoms practically unchanged but leads to a surprising bond shortening in the S...S and P...P cases. These seemingly contradictory effects are rationalized through a qualitative analysis based on an elementary molecular orbital description of three-electron bonding.

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Accession: 046676929

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PMID: 11878994

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