Reactions of Five-Membered Metallacyclocumulenes Cp2M(畏4-t-Bu-C4-t-Bu) (M = Ti, Zr) with Diisobutylaluminum Hydride

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• 作者：Vladimir V. Burlakov ; Katharina Kaleta ; Torsten Beweries ; Perdita Arndt ; Wolfgang Baumann ; Anke Spannenberg ; Vladimir B. Shur ; Uwe Rosenthal
• 刊名：Organometallics
• 出版年：2011
• 出版时间：March 14, 2011
• 年：2011
• 卷：30
• 期：5
• 页码：1157-1161
• 全文大小：792K
• 年卷期：v.30,no.5(March 14, 2011)
• ISSN：1520-6041

文摘

Reactions of the five-membered metallacyclocumulenes Cp₂M(畏⁴-t-Bu-C₄-t-Bu) (M = Ti, Zr) with the Lewis Acid i-Bu₂AlH were studied. Cp₂Ti(畏⁴-t-Bu-C₄-t-Bu) (1) reacts with i-Bu₂AlH to give a heterobimetallic complex which was isolated as the THF adduct Cp₂Ti[渭-畏¹:畏²-t-BuCC鈭扖HC-t-Bu)(渭-H)(i-BuAl)(THF)] (4). The reaction of the corresponding zirconocene compound Cp₂Zr(畏⁴-t-Bu-C₄-t-Bu) (2) with i-Bu₂AlH results in a cleavage of the central C鈺怌 bond of the metallacyclocumulene C₄ chain and formation of the dinuclear complex 6 and the dinuclear acetylide [(Cp₂Zr)₂(渭-C鈮-t-Bu)₂]. In addition to the formation of 6 and the acetylide species an elimination of the butadiyne takes place, which gives in the subsequent interaction with i-Bu₂AlH the zwitterionic aluminum cluster 7. Alternatively, complex 7 is also formed in the direct reaction of the butadiyne with a 3-fold excess of i-Bu₂AlH. The molecular structures of 4 and 7 were confirmed by X-ray analysis.