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Reaction of Silicon Atoms with Acetylene and Ethylene: Generation and Matrix‐Spectroscopic Identification of C 2 H 2 Si and C 2 H 4 Si Isomers
Author(s) -
Maier Günther,
Reisenauer Hans Peter,
Egenolf Heiko
Publication year - 1998
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199807)1998:7<1313::aid-ejoc1313>3.0.co;2-k
Subject(s) - acetylene , chemistry , matrix isolation , ethylene , silicon , photochemistry , silylene , ab initio , hydrogen , infrared spectroscopy , organic chemistry , catalysis
Evaporation of silicon and consecutive cocondensation of the generated atoms with acetylene or ethylene in an argon matrix turnes out to be a new access to C 2 H 2 Si and C 2 H 4 Si isomers, respectively. In both cases the silicon atoms rather add to the π system than insert into C–H bonds, leading to cyclic silylenes as primary reaction products. In the Si/acetylene system the primary product is silacyclopro‐penylidene ( 2 ), which shows the already known photo‐chemical interconversion into additional C 2 H 2 Si species. On the other hand, cocondensation of silicon atoms with ethylene and subsequent irradiation lead to the matrix‐isolation of three new C 2 H 4 Si isomers [apart from the known silacyclopropene ( 7 ) and silylacetylene ( 8 )], namely silacyclopropylidene ( 10 ), s ‐ trans ‐vinylsilylene ( 11 ), and the unsubstituted 1‐silaallene ( 13 ). These species can be identified by comparison of their experimental IR spectra and those obtained by ab initio calculations. In a second reaction path, SiH 2 , which is formed as a byproduct from atomic silicon and hydrogen impurities, adds to the π system of acetylene, yielding silacyclopropene ( 7 ). Silacyclopropane ( 16 ), the analogous product of the reaction of SiH 2 with ethylene, could not be observed.