Reactivity of Phosphanylphosphinidene Complex of Tungsten(VI) toward Phosphines: A New Method of Synthesis of catena-Polyphosphorus Ligands

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• 作者：Rafa艂 Grubba ; Anna Ordyszewska ; Kinga Kaniewska ; 艁ukasz Ponikiewski ; Jaros艂aw Chojnacki ; Dietrich Gudat ; Jerzy Pikies
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：September 8, 2015
• 年：2015
• 卷：54
• 期：17
• 页码：8380-8387
• 全文大小：460K
• ISSN：1520-510X

文摘

The reactivity of an anionic phosphanylphosphinidene complex of tungsten(VI), [(2,6-i-Pr₂C₆H₃N)₂(Cl)W(畏²-t-Bu₂P鈺怭)]Li路3DME toward PMe₃, halogenophosphines, and iodine was investigated. Reaction of the starting complex with Me₃P led to formation of a new neutral phosphanylphosphinidene complex, [(2,6-i-Pr₂C₆H₃N)₂(Me₃P)W(畏²-t-Bu₂P鈺怭)]. Reactions with halogenophosphines yielded new catena-phosphorus complexes. From reaction with Ph₂PCl and Ph₂PBr, a complex with an anionic triphosphorus ligand t-Bu₂P鈥揚^(鈭?鈥揚Ph₂ was isolated. The main product of reaction with PhPCl₂ was a tungsten(VI) complex with a pentaphosphorus ligand, t-Bu₂P鈥揚^(鈭?鈥揚(Ph)鈥揚^(鈭?鈥揚-t-Bu₂. Iodine reacted with the starting complex as an electrophile under splitting of the P鈥揚 bond in the t-Bu₂P鈺怭 unit to yield [(1,2-畏-t-Bu₂P鈥揚鈥揚-t-Bu₂)W(2,6-i-Pr₂C₆H₃N)₂Cl], t-Bu₂PI, and phosphorus polymers. The molecular structures of the isolated products in the solid state and in solution were established by single crystal X-ray diffraction and NMR spectroscopy.