Open AccessSyntheses and Molecular Structures of Liquid Pyrophoric Hydridosilanes
Author(s) -
Gerwig Maik,
Böhme Uwe,
Friebel Mike,
Gründler Franziska,
Franze Georg,
Rosenkranz Marco,
Schmidt Horst,
Kroke Edwin
Publication year - 2020
Publication title -
chemistryopen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.644
H-Index - 29
ISSN - 2191-1363
DOI - 10.1002/open.202000152
Subject(s) - diffractometer , radical , electron paramagnetic resonance , silanes , chemistry , crystallization , crystallography , electron diffraction , ultraviolet , crystal structure , diffraction , photochemistry , materials science , organic chemistry , silane , nuclear magnetic resonance , optics , optoelectronics , physics
Trisilane, isotetrasilane, neopentasilane, and cyclohexasilane have been prepared in gram scale. In‐situ cryo crystallization of these pyrophoric liquids in sealed capillaries on the diffractometer allows access to the single crystal structures of these compounds. Structural parameters are discussed and compared to gas‐phase electron diffraction structures from literature and with the results from quantum chemical calculations. Significantly higher packing indices are found for the silanes compared to the corresponding alkanes. Radiation with ultraviolet light (365 nm) and parallel ESR (EPR) measurement shows that cyclohexasilane is easily split into radicals, which subsequently leads to the formation of branched and chain‐like oligomers. The other compounds form no radicals under these conditions. NMR spectra of all four compounds have been recorded.