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Density Functional Study of the Complexation Reaction of Sn(CH 3 ) 3 X (X = F, Cl, Br and I) with Halide Anions
Author(s) -
De Proft Frank,
VivasReyes Ricardo,
Biesemans Monique,
Willem Rudolph,
Martin Jan M. L.,
Geerlings Paul
Publication year - 2003
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200300044
Subject(s) - chemistry , hsab theory , electronegativity , density functional theory , polarizability , halogen , lewis acids and bases , halide , computational chemistry , polarizable continuum model , coupling constant , inorganic chemistry , molecule , solvation , organic chemistry , catalysis , quantum mechanics , physics , alkyl
The Lewis acid‐base reaction between Sn(CH 3 ) 3 X and Y − (with X, Y = F, Cl, Br and I) has been studied using quantum chemical calculations. Complexation energies were calculated at the Density Functional Theory (DFT) level and rationalized on the basis of a local application of the hard and soft acids and bases principle. It was observed that smaller differences in the local softness of the interacting sites in the Lewis acid and base correspond to stronger interactions. Moreover, the calculated sequences in complexation energies can be reproduced using equations containing chemical concepts introduced within the framework of conceptual density functional theory and rooted in the hard and soft acids and bases principle and referring only to the reactants. A method of treating the electronegativity and softness of the halide anions is presented based on a Taylor expansion of the electronegativity of the neutral halogens and the softness‐polarizability proportionality. Experimental evidence for the calculated sequences was gathered from measured 117 Sn chemical shifts and 1 J ( 13 C‐ 119/117 Sn) coupling constant changes upon complexation. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)