Molecular structure of 1,1,2,2-tetra-tert-butyldisilane: unusual structural motifs in sterically crowded disilanes

Dalton Transactions : an International Journal of Inorganic Chemistry
Sarah L HinchleyKarl Hassler

Abstract

The molecular structure of 1,1,2,2-tetra-tert-butyldisilane has been determined by gas-phase electron diffraction supported by ab initio calculations, in the solution phase by Raman spectroscopy, and in the solid phase by Raman spectroscopy and X-ray crystallography. The gas-phase structure (C2 symmetry) was found to be almost anticlinal, a most unusual and unexpected result. In the favoured conformation, contact between tert-butyl groups at each end of the molecule is avoided by a large deviation of the angles around the silicon atoms from the parent tetrahedral angle of 109.5 degrees. In fact, the Si-Si-C angles returned from the gas electron diffraction refinement are 117.0(5) and 110.7(6) degrees, indicating the large degree of flexibility about the silicon centres. The ab initio methods and gas electron diffraction results indicate that there is only one conformer of But2HSiSiHBut2 in the gaseous mixture. Variable temperature Raman studies indicate the possibility of a further higher energy conformer existing in the liquid phase. However, this seems quite improbable from other observations made for the Raman spectra at all temperatures. The X-ray structure is close to that observed in the gas phase, with phiHSiSiH = 94.2(1...Continue Reading

Citations

Jun 21, 2007·Chemical Communications : Chem Comm·Sarah L MastersKarl Hassler
Feb 23, 2010·Chemistry : a European Journal·Birgit PrügerKarl Anker Jørgensen
Aug 11, 2004·Dalton Transactions : an International Journal of Inorganic Chemistry·Sarah L HinchleyAlan H Cowley
Jan 30, 2020·Chemical Communications : Chem Comm·Marvin LinnemannstönsNorbert W Mitzel
Nov 2, 2019·Angewandte Chemie·Samuel J PlamondonJames L Gleason
Jul 9, 2016·Expert Opinion on Drug Metabolism & Toxicology·Tatiana TverdohlebNebojsa Nick Knezevic
Dec 21, 2019·Chemistry : a European Journal·Marvin LinnemannstönsNorbert W Mitzel

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