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Article

The Si−Si Effect on Ionization of β-Disilanyl Sulfides and Selenides

Supporting Info

Richard S. Glass,*^† Eric Block,^‡ Edward Lorance,^§ Uzma I. Zakai,^† Nadine E. Gruhn,^† Jin Jin,^‡ and Shao-Zhong Zhang^‡

Contribution from the Departments of Chemistry, The University of Arizona, Tucson, Arizona 85721, University at Albany, State University of New York, Albany, New York 12222, and Vanguard University, Costa Mesa, California 92626

J. Am. Chem. Soc., 2006, 128 (39), pp 12685–12692

DOI: 10.1021/ja0573514

Publication Date (Web): September 13, 2006

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

†

The University of Arizona.

‡

University at Albany.

Vanguard University.

, rglass@u.arizona.edu

Abstract

The ionization energies of conformationally constrained, newly synthesized β-disilanyl sulfides and selenides were determined by photoelectron spectroscopy. These ionization energies reflect substantial (0.53−0.75 eV) orbital destabilizations. The basis for these destabilizations was investigated by theoretical calculations, which reveal geometry-dependent interaction between sulfur or selenium lone pair orbitals and σ-orbitals, especially Si−Si σ-orbitals. These results presage facile redox chemistry for these compounds and significantly extend the concept of σ-stabilization of electron-deficient centers.

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