2,3-Diphosphino-1,4-diphosphonium Ions

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• 作者：Yuen-ying Carpenter ; C. Adam Dyker ; Neil Burford ; Michael D. Lumsden ; Andreas Decken
• 刊名：Journal of the American Chemical Society
• 出版年：2008
• 出版时间：November 19, 2008
• 年：2008
• 卷：130
• 期：46
• 页码：15732-15741
• 全文大小：274K
• 年卷期：v.130,no.46(November 19, 2008)
• ISSN：1520-5126

文摘

Salts of the first crystallographically characterized chlorophosphinophosphonium ions have been prepared, and their reaction with Ph₃P results in reductive coupling of the chlorophosphine centers to give the first acyclic 2,3-diphosphino-1,4-diphosphonium ions, representing a key framework in the development of catena-phosphorus chemistry. These new salts of general formula [R₃P-PR′-PR′-PR₃][OTf]₂ are also obtained in a one-pot diastereoselective reaction of a dichlorophosphine, a tertiary phosphine, and trimethylsilyltrifluoromethanesulfonate. The structural and spectroscopic features of the new dications complement those of the known diphosphonium and 2-phosphino-1,3-diphosphonium dications. Quantitative ligand exchange reactions are observed when derivatives of [Ph₃P-PR′-PR′-PPh₃][OTf]₂ are combined with Me₃P, demonstrating the coordinative nature of the phosphine−phosphonium P−P bonds and implicating a bonding model involving the diphosphenium dication acceptor. The observed solid state structures have been interpreted in the context of computational studies.