Premium
Hydroalumination of Silicon Centered Dialkynes – Synthesis of Mixed Alkenyl‐Alkinylsilanes
Author(s) -
Uhl Werner,
Heller Denis
Publication year - 2010
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200900323
Subject(s) - chemistry , intramolecular force , geminal , silanes , trimethylsilyl , steric effects , double bond , aluminium , triple bond , medicinal chemistry , silicon , stereochemistry , polymer chemistry , organic chemistry , silane
Bis(phenylethynyl)silanes reacted with equimolar quantities of various dialkylaluminium hydrides, R 2 Al–H [R = CH 2 t Bu, t Bu, i Bu, CH(SiMe 3 ) 2 ], by hydroalumination and addition of a Al–H bond to a C≡C triple bond. Alkenyl‐alkynylsilanes were formed, which had the aluminium atoms in geminal positions with the silicon atoms and adopt a cis arrangement of aluminium and hydrogen at the resulting C=C double bonds in most cases. cis / trans ‐Rearrangement with the formation the trans ‐addition products was observed only for the two sterically least shielded compounds. Intramolecular interactions of the coordinatively unsaturated aluminium atoms with the α‐carbon atoms of the intact alkynyl groups were detected by crystal structure determinations for the tert ‐butyl and neopentyl derivatives, whereas they did not occur with bulky bis(trimethylsilyl)methyl substituents.