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Elucidation of the thermochemical properties of triphenyl- or tributyl-substituted Si-, Ge-, and Sn-centered radicals by means of electrochemical approaches and computations
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Physical Chemistry (closed 20110630).ORCID iD: 0000-0003-2673-075X
2005 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 127, no 8, 2677-2685 p.Article in journal (Refereed) Published
Abstract [en]

Redox potentials of a number of triphenyl- or tributyl-substituted Si-, Ge-, or Sn-centered radicals, R3M., have been measured in acetonitrile, tetrahydrofuran, or dimethyl sulfoxide by photomodulated voltammetry or through a study of the oxidation process of the corresponding anions in linear sweep voltammetry. For the results pertaining to the Ph3M. series (including literature data for M = C), the order of reduction potentials follows Sn > Ge > C > Si, while for the two oxidation potentials, it is C > Si. The effect of the R group on the redox properties of R3Sn. is pronounced in that the reduction potential is more negative by 490 mV in tetrahydrofuran (390 mV in dimethyl sulfoxide) when R is a butyl rather than a phenyl group. The experimental trends have been substantiated through quantum chemical calculations, and they can be explained qualitatively by considering a combination of effects, such as charge capacity being most pronounced for the heavier elements, resonance stabilization present for the planar Ph3C. and all R3M+, and finally a contribution from solvation. The solvation of R3M- is observed to be relatively strong because of a rather localized negative charge in the pyramidal geometry. However, there is no evidence in the calculations to support the existence of covalent interactions between solvent and anions. The solvation of R3M+ is relatively weak, which may be attributed to the planar geometry around the center atom, leading to more spread out charge than that for a pyramidal geometry. Although the calculated solvation energies based on the polarizable continuum model approach exhibit the expected trends, they are not able to reproduce the experimentally derived values on a detailed level for these types of ions. An evaluation of the general performance of the continuum model is provided on the basis of present and previous studies.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2005. Vol. 127, no 8, 2677-2685 p.
Keyword [en]
effective core potentials, polarizable continuum model, bond-dissociation energies, transient free-radicals, reduction potentials, molecular calculations, electroreductive synthesis, dimethylsulfoxide solution, population analysis, acceptor molecules
National Category
Physical Chemistry
URN: urn:nbn:se:kth:diva-14564DOI: 10.1021/ja044687pISI: 000227308100054ScopusID: 2-s2.0-14744279275OAI: diva2:332605

QC 20100525

Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2014-08-29Bibliographically approved

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Brinck, Tore
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