Reactivities of Indenylruthenium Complex toward Internal Alkynes: Formation of Disubstituted Vinylidene Complexes and Indenyl鈥揂lkyne Coupling

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• 作者：Yousuke Ikeda ; Yuichiro Mutoh ; Kohei Imai ; Noriko Tsuchida ; Keiko Takano ; Youichi Ishii
• 刊名：Organometallics
• 出版年：2013
• 出版时间：August 12, 2013
• 年：2013
• 卷：32
• 期：15
• 页码：4353-4358
• 全文大小：324K
• 年卷期：v.32,no.15(August 12, 2013)
• ISSN：1520-6041

文摘

Reaction of the indenylruthenium complex [(畏⁵-C₉H₇)RuCl(dppe)] with internal alkynes (MeC鈮R, R = Et, Ph) in the presence of NaBAr^F₄ gives rise to two types of C鈥揅 bond activation, i.e., alkyne insertion/尾-carbon elimination and internal alkyne/disubstituted vinylidene rearrangement, as reversible processes. At 70 掳C, regioisomeric complexes [Ru{C(Me)鈺怌(R)鈥?畏⁶-C₉H₇)}(dppe)][BAr^F₄] (2) and [Ru{C(R)鈺怌(Me)鈥?畏⁶-C₉H₇)}(dppe)][BAr^F₄] (2鈥?/b>) are formed through insertion of the alkyne into the Ru鈥搃ndenyl bond followed by haptotropic rearrangement. Complexes 2鈥?/b> isomerize completely to 2 at this temperature after longer reaction time. At 130 掳C, 2 are further converted into the disubstituted vinylidene complexes [(畏⁵-C₉H₇)Ru{鈺怌鈺怌(R)Me}(dppe)][BAr^F₄] (3) through alkyne鈥搗inylidene rearrangement of the 畏²-alkyne intermediate. This provides a rare example of direct observation of the 尾-carbon elimination from an unstrained transition metal alkenyl complex.