Engineering topics

Ferguson, John T.

Publications and source records attributed to Ferguson, John T..

2 records

DOE OSTI2021

Isolation of a Cyclopentasilane from Magnesium Reduction of a Linear Hexasilane

The reductive cyclization of two linear hexasilanes is contrasted, where a methylated precursor yielded a cyclohexasilane while the tert-butyl-functionalized analog unexpectedly yielded a cyclopentasilane. A comprehensive analysis using X-ray diffraction, IR, HR, HRMS, and multinuclear (1H, 13C and 29Si) 1D and 2D NMR spectroscopy identified the 1,2-dihydrodisilane tBuPhHSi–SiHPhtBu as an additional product, which was interpreted as supportive of a mechanism involving silylene elimination. Here, the results of this study may prove informative about substituent effects in the practice of complex organosilicon molecular synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Long-range coupling in cyclic silanes

We report the synthesis of a mixed methyl- and hydro-substituted cyclosilane (1) possessing cis/trans stereoisomerism. Each diastereomer of 1 possesses distinct symmetry elements (cis-1: Cs-symmetric; trans-1: C 2 -symmetric). Cyclosilane 1 is a model system to probe configuration- and conformation-dependent long-range proton–proton coupling. Here, extensive NMR spectroscopic characterization is reported, including one-dimensional 1 H NMR and 29 Si DEPT and INEPT+ spectra and two-dimensional 1 H– 29 Si and 1 H– 1 H correlated spectroscopy (HSQC, HMBC, COSY). On the basis of these experiments, molecular connectivity consistent with four-bond 1 H– 1 H coupling is confirmed.

36 MATERIALS SCIENCE↗