New Synthetic Procedures to Catena-Phosphorus Cations: Preparation and Dissociation of the First cyclo-Phosphino-halophosphonium Salts

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• 作者：Jan J. Weigand ; Neil Burford ; Reagan J. Davidson ; T. Stanley Cameron ; Patrick Seelheim
• 刊名：Journal of the American Chemical Society
• 出版年：2009
• 出版时间：December 16, 2009
• 年：2009
• 卷：131
• 期：49
• 页码：17943-17953
• 全文大小：501K
• 年卷期：v.131,no.49(December 16, 2009)
• ISSN：1520-5126

文摘

Chlorination of 1,2,3,4-tetracyclohexyl-cyclo-tetraphosphine (2) by PhICl₂ or PCl₅ in the presence of Me₃SiOTf or GaCl₃ provides a stepwise approach to salts of the first cyclo-phosphino-chlorophosphonium cations [Cy₄P₄Cl]⁺ ([19]⁺) and [Cy₄P₄Cl₂]²⁺ ([20]²⁺). The analogous iodo derivative [Cy₄P₄I]⁺ ([17]⁺) is obtained as the tetraiodogallate salt from reaction of 2 with I₂ in the presence of GaI₃. Reactions of the dication [20]²⁺ with PMe₃ or dmpe effect a dissociation of the cyclic framework resulting in the formation of salts containing [Me₃PPCyPCyPMe₃]²⁺ ([27]²⁺), [dmpeCyP]²⁺ ([29]²⁺), and [dmpeCyPCyP]²⁺ ([30]²⁺), respectively. The new cations represent phosphine complexes of the [PCy]²⁺ and [P₂Cy₂]²⁺ cationic fragments from [20]²⁺, demonstrating the coordinate nature of the phosphinophosphonium bonds in cyclo-phosphino-halophosphonium cations. The compounds have been characterized by NMR spectroscopy, single crystal X-ray crystallography, and Raman spectroscopy.