Synthesis, structure, reactions, and photoelectron spectra of new mixed sulfur-, selenium- or tellurium and silicon- or tin-containing heterocycles



More than 40 new 4- to 12-membered ring heterocycles containing various combinations of Group 14 elements (Si and Sn) and Group 16 elements (S, Se, and Te) have been synthesized and fully characterized. Synthesis of these small-ring as well as medium-ring (mesocyclic) heterocycles from α, ω-dihalides was facilitated by the presence of gem-dialkylsilyl and gem-dialkylstannyl groups in the precursors. Solid-state conformations of the new ring systems have been determined by X-ray crystallography. Oxidation of mixed S(Se, Te)/Si eight-membered ring mesocycles as well as 1,5-dithia-, 1,5-diselena-, and 1,5-ditelluracyclooctane with NOPF6 gave dications, which can be characterized by NMR. On treatment with nucleophiles, mesocyclic dications or the corresponding radical cations underwent ring contraction to give five- or six-membered ring heterocycles. The ionization energies of the above conformationally constrained 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 suggest facile redox chemistry for these compounds and significantly extend the concept of σ-stabilization of electron-deficient centers. © 2007 Wiley Periodicals, Inc. 18:509–515, 2007; Published online in Wiley InterScience ( DOI 10.1002/hc.20333