Reactions of Osmium Carbyne Complexes OsCl3(≡CR)(PPh3)2 (R = CH═CPh2, CH2Ar) with Bromine and Hydrogen Peroxide

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• 作者：Wei Bai ; Ka-Ho LeeWai Yiu Hung ; Herman H. Y. Sung ; Ian D. Williams ; Zhenyang Lin ; Guochen Jia
• 刊名：Organometallics
• 出版年：2017
• 出版时间：February 13, 2017
• 年：2017
• 卷：36
• 期：3
• 页码：657-664
• 全文大小：574K
• ISSN：1520-6041

文摘

The reactions of the trichloro carbyne complexes OsCl₃(≡CR)(PPh₃)₂ (R = CH═CPh₂, CH₂Ar) with bromine and hydrogen peroxide were studied. Unlike monochloro carbyne complexes OsCl(≡CAr)(CO)(PPh₃)₂, the trichloro complexes OsCl₃(≡CR)(PPh₃)₂ do not undergo oxidation reactions at the metal center or the metal–carbyne bond. Treatment of OsCl₃(≡CCH═CPh₂)(PPh₃)₂ with Br₂/H₂O and H₂O₂/HCl produced OsBr₃(≡CCH═CPh₂)(H₂O)(PPh₃) and OsCl₃(≡CCCl═CPh₂)(PPh₃)₂, respectively. Reactions of OsCl₃(≡CCH₂-C₆H₄-p-R)(PPh₃)₂ (R = H, CMe₃) with H₂O₂/HCl or H₂O₂ gave OsCl₃{≡CC(O)-C₆H₄-p-R}(PPh₃)₂. Computational studies suggest that the difference in the reactivity of OsCl(≡CAr)(CO)(PPh₃)₂ and OsCl₃(≡CR)(PPh₃)₂ is mainly of thermodynamic origin.