Unusual Reactivities of Linear Disilanes with o-Carboranyl Unit

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• 作者：Young-Joo Lee ; Jong-Dae Lee ; Sung-Joon Kim ; Byung Woo Yoo ; Jaejung Ko ; Il-Hwan Suh ; Minserk Cheong ; and Sang Ook Kang
• 刊名：Organometallics
• 出版年：2004
• 出版时间：February 2, 2004
• 年：2004
• 卷：23
• 期：3
• 页码：490 - 497
• 全文大小：231K
• 年卷期：v.23,no.3(February 2, 2004)
• ISSN：1520-6041

文摘

The linear disilanes 1,2-bis(1'-R-o-carboranyl)-1,1,2,2-tetramethyl-1,2-disilane (R = H (2a),Me (2b), Ph (2c)) were prepared by reacting the lithium salt of 1-R-o-carborane (1) with1,2-dichlorotetramethyldisilane. These linear disilanes (2) were found to be useful precursorsfor the synthesis of a variety of cyclic compounds. For instance, reaction of the lineardilithiodisilane 2a with 1,2-dichlorotetramethyldisilane afforded the four-membered cycliccompound 3,4-o-carboranylene-1,1,2,2-tetramethyl-1,2-disilacyclobutane (3). Further, whereasthe reaction of linear disilane (2a) with Pt(PEt₃)₃ was found to yield the cyclic bis(silyl)platinum complex 4, the reaction of the methyl-o-carboranyl-substituted disilane 2b withPt(PEt₃)₃ under the same conditions yielded the decomposed bis(silyl)platinum complex 5,formed via oxidative addition of a Si-Si bond at the platinum atom. The reaction of thecyclic disilane 3 using a catalytic amount of lithium metal afforded a five-membered cyclictrisilyl compound (6). The reaction of 6 with phenylacetylene in the presence of a catalyticamount of Pd(CNBu^t)₂ was found to yield the seven-membered trisilyl ring compound 6,7-o-carboranylene-1,1,4,4,5,5-hexamethyl-2-phenyl-1,4,5-trisilacyclohept-2-ene (7). The structures of compounds 2a,b, 4-6, and 7 were determined using single-crystal X-ray crystallography.