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Silylene Reactions with Buta‐1,3‐diynes: Cycloadditions, Insertions, and Rearrangements
Author(s) -
Ostendorf Detlev,
Kirmaier Lars,
Saak Wolfgang,
Marsmann Heinrich,
Weidenbruch Manfred
Publication year - 1999
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199912)1999:12<2301::aid-ejic2301>3.0.co;2-e
Subject(s) - chemistry , silylene , photodissociation , cyclobutane , hexa , irradiation , medicinal chemistry , photochemistry , stereochemistry , diene , cis–trans isomerism , organic chemistry , silicon , ring (chemistry) , physics , nuclear physics , natural rubber
Di‐ tert ‐butylsilylene, generated by photolysis of hexa‐ tert ‐butylcyclotrisilane 1 or 1,1‐di‐ tert ‐butyl‐ trans ‐2,3‐dimethyl‐silirane ( 2 ), reacts with the 1,3‐diyne ( t Bu–C≡C–) 2 9 to furnish the dialkynylsilane 11 via the isolable alkynylsilirene 10 . Photolysis of excess 1 in the presence of 9 furnishes the C–C linked 2,2′‐disilirene 12 which, upon prolonged irradiation, rearranges to the 2,5‐disilabicyclo[2.2.0]hexa‐1(6),3‐diene ( 13 ). Treatment of 9 with diarylsilylenes, formed by irradiation of hexamethyl‐2,2‐dimesityltrisilane ( 3 ) or hexamethyl‐2,2‐bis(2,4,6‐triisopropylphenyl)trisilane ( 4 ), gives the corresponding alkynylsilirenes 14 and 15 , respectively. Photolysis of 1 or 2 in the presence of (Me 3 Si–C≡C–) 2 16 yields the dialkynylsilane 17 which, on further reaction with 2 , yields the 2,5‐disilabicyclo[2.2.0]hexa‐1(6),3‐diene ( 18 ). Irradiation of 3 in the presence of 16 affords the cis ‐ and trans ‐isomeric 1,3‐dimethylene‐2,4‐disila‐cyclobutane derivatives cis ‐ 21 and trans ‐ 21 , presumably via a 1‐silaallene intermediate. The structures of 12 , 15 , 18 , cis ‐ 21 , and trans ‐ 21 have been determined by X‐ray crystallography.