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

Eric Block, Richard S Glass, Evgeny V. Dikarev, Nadine E. Gruhn, Jin Jin, Bo Li, Edward Lorance, Uzma I. Zakai, Shao Zhong Zhang

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

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 αa, ω-dihalides was facilitated by the presence of gemdialkylsilyl 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 orbitais 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.

Original languageEnglish (US)
Pages (from-to)509-515
Number of pages7
JournalHeteroatom Chemistry
Volume18
Issue number5
DOIs
StatePublished - 2007

Fingerprint

Tellurium
Tin
Ionization potential
Silicon
Selenium
Photoelectrons
Sulfur
Chalcogens
Gems
Nucleophiles
X ray crystallography
Sulfides
Photoelectron spectroscopy
Conformations
Cations
Stabilization
Nuclear magnetic resonance
Oxidation
Geometry
Electrons

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Synthesis, structure, reactions, and photoelectron spectra of new mixed sulfur-, selenium- Or tellurium and silicon- Or tin-containing heterocycles. / Block, Eric; Glass, Richard S; Dikarev, Evgeny V.; Gruhn, Nadine E.; Jin, Jin; Li, Bo; Lorance, Edward; Zakai, Uzma I.; Zhang, Shao Zhong.

In: Heteroatom Chemistry, Vol. 18, No. 5, 2007, p. 509-515.

Research output: Contribution to journalArticle

Block, Eric ; Glass, Richard S ; Dikarev, Evgeny V. ; Gruhn, Nadine E. ; Jin, Jin ; Li, Bo ; Lorance, Edward ; Zakai, Uzma I. ; Zhang, Shao Zhong. / Synthesis, structure, reactions, and photoelectron spectra of new mixed sulfur-, selenium- Or tellurium and silicon- Or tin-containing heterocycles. In: Heteroatom Chemistry. 2007 ; Vol. 18, No. 5. pp. 509-515.
@article{c63d8e45e14e4da6b81a3f3adbdf101f,
title = "Synthesis, structure, reactions, and photoelectron spectra of new mixed sulfur-, selenium- Or tellurium and silicon- Or tin-containing heterocycles",
abstract = "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 αa, ω-dihalides was facilitated by the presence of gemdialkylsilyl 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 orbitais 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.",
author = "Eric Block and Glass, {Richard S} and Dikarev, {Evgeny V.} and Gruhn, {Nadine E.} and Jin Jin and Bo Li and Edward Lorance and Zakai, {Uzma I.} and Zhang, {Shao Zhong}",
year = "2007",
doi = "10.1002/hc.20333",
language = "English (US)",
volume = "18",
pages = "509--515",
journal = "Heteroatom Chemistry",
issn = "1042-7163",
publisher = "Wiley-Blackwell",
number = "5",

}

TY - JOUR

T1 - Synthesis, structure, reactions, and photoelectron spectra of new mixed sulfur-, selenium- Or tellurium and silicon- Or tin-containing heterocycles

AU - Block, Eric

AU - Glass, Richard S

AU - Dikarev, Evgeny V.

AU - Gruhn, Nadine E.

AU - Jin, Jin

AU - Li, Bo

AU - Lorance, Edward

AU - Zakai, Uzma I.

AU - Zhang, Shao Zhong

PY - 2007

Y1 - 2007

N2 - 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 αa, ω-dihalides was facilitated by the presence of gemdialkylsilyl 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 orbitais 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.

AB - 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 αa, ω-dihalides was facilitated by the presence of gemdialkylsilyl 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 orbitais 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.

UR - http://www.scopus.com/inward/record.url?scp=34547219051&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=34547219051&partnerID=8YFLogxK

U2 - 10.1002/hc.20333

DO - 10.1002/hc.20333

M3 - Article

AN - SCOPUS:34547219051

VL - 18

SP - 509

EP - 515

JO - Heteroatom Chemistry

JF - Heteroatom Chemistry

SN - 1042-7163

IS - 5

ER -