Preparation of Osmium η3-Allenylcarbene Complexes and Their Uses for the Syntheses of Osmabenzyne Complexes

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• 作者：Ting Bin Wen ; Ka-Ho Lee ; Jiangxi Chen ; Wai Yiu Hung ; Wei Bai ; Huacheng Li ; Herman H. Y. Sung ; Ian D. Williams ; Zhenyang Lin ; Guochen Jia
• 刊名：Organometallics
• 出版年：2016
• 出版时间：May 23, 2016
• 年：2016
• 卷：35
• 期：10
• 页码：1514-1525
• 全文大小：730K
• 年卷期：0
• ISSN：1520-6041

文摘

Treatment of OsCl₂(PPh₃)₃ with HC≡CAr (Ar = Ph, p-tolyl) produced the η³-allenylcarbene complexes OsCl₂(═CAr-η²-CH═C═CHAr)(PPh₃)₂. Reactions of the η³-allenylcarbene complexes with gold alkynyls Au(C≡CR)(PPh₃) (R = Ph, p-tolyl, TMS, ⁿBu, CH(OEt)₂) or copper(I) alkynyls Cu(C≡CR) (R = Ph, TMS) in the presence of HNEt₃Cl produced the osmabenzynes Os{≡CC(R)═C(CH₂Ar)CH═CAr}Cl₂(PPh₃)₂. Computational studies suggest that the osmabenzynes are formed through electrocyclization of osmium alkynyl-allenylcarbene intermediates followed by protonation with HNEt₃Cl.