- Air-Stable Tetrakis(2,4,6-triisopropylphenyl)disilene. Direct Synthesis of Disilene from Dihalomonosilane
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The most air-stable disilene, tetrakis(2,4,6-triisopropylphenyl)disilene was obtained by the direct treatment of dichloromonosilane, bis(2,4,6-triisopropylphenyl)dichlorosilane, with lithium naphthalenide.The Si=Si bond, The distance being 2.144 Angstroem
- Watanabe, Hamao,Takeuchi, Ken,Fukawa, Norio,Kato, Motohiko,Goto, Midori,Nagai, Yoichiro
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- Silicon compounds with strong intramolecular steric interactions, 71. Silylene reactions with buta-1,3-diynes: Cycloadditions, insertions, and rearrangements
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Di-tert-butylsilylene, generated by photolysis of hexa-tert- butylcyclotrisilane 1 or 1,1-di-tert-butyl-trans-2,3-dimethylsilirane (2), reacts with the 1,3-diyne (tBu-C≡C-)2 9 to furnish the dialkynylsilane 11 via the isolable alkynylsilirene 10. Photolysis of excess I 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 (Me3Si-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- disilacyclobutane 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.
- Ostendorf, Detlev,Kirmaier, Lars,Saak, Wolfgang,Marsmann, Heinrich,Weidenbruch, Manfred
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p. 2301 - 2307
(2007/10/03)
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- The First Preparation of Disilene via Reductive Dehalogenation of 1,2-Dichlorodisilane. The Formation of an Unusual Air-Oxidation Product, 1-Oxa-2-silacyclopent-3-ene Derivative
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The most air-stable disilene, tetrakis(2,4,6-triisopropylphenyl)disilene, again was obtained by the reaction of 1,2-dichloro-1,1,2,2-tetrakis(2,4,6-triisopropylphenyl)disilane with lithium naphthalenide.The disilene afforded its air-oxidation product havi
- Watanabe, Hamao,Takeuchi, Ken,Nakajima, Kenji,Nagai, Yoichiro,Goto, Midori
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p. 1343 - 1346
(2007/10/02)
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