Abstract
AbstractBis(phenylethynyl)silanes reacted with equimolar quantities of various dialkylaluminium hydrides, R2Al–H [R = CH2tBu, tBu, iBu, CH(SiMe3)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.
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