The First Structurally Characterized Metal (κ2N,P)-Phosphinohydrazides: The Key to Understanding the Intramolecular Rearrangement R2P−NR′

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• 作者：Alexander N. Kornev ; Natalia V. Belina ; Vyacheslav V. Sushev ; Georgy K. Fukin ; Evgenii V. Baranov ; Yuriy A. Kurskiy ; Andrei I. Poddelskii ; Gleb A. Abakumov ; Peter Lnnecke ; Evamarie Hey-Hawkins
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：June 15, 2009
• 年：2009
• 卷：48
• 期：12
• 页码：5574-5583
• 全文大小：840K
• 年卷期：v.48,no.12(June 15, 2009)
• ISSN：1520-510X

文摘

A number of novel phosphinohydrazines, iPr₂P−NPh−NPh−H (1), iPr₂P−NH−NH−PiPr₂ (2), iPr₂P−NMe−NH−PiPr₂ (3), and H−NMe−NH−PiPr₂ (4), were prepared and characterized. The interaction of 1 with 1 equiv of n-BuLi afforded a complex compound [Li(DME)₃][Li{(NPh−NPh−PiPr₂)-κN}₂] (5). The reaction of 5 with NiBr₂ resulted in the formation of the first stable transition metal phosphinohydrazide [Ni{(NPh−NPh−PiPr₂)-κ²N,P}₂] (6). Similarly, the cobalt(II) derivative [Co{(NPh−NPh−PiPr₂)-κ²N,P}₂] (7) was prepared by the reaction of 1 with Co[N(SiMe₃)₂]₂. An X-ray study reveals formation of the complexes containing elongated N−N bonds (1.443(1), 1.466(2), and 1.470(2) Å for 5, 6, and 7, respectively) as compared with the starting material 1 (1.407(1) Å). Nickel phosphinohydrazide 6 has a square-planar cis configuration; the cobalt complex 7 possesses a square-planar centrosymmetric trans configuration. The half-sandwich nickel(II) complex [CpNi{(NPh−NPh−PiPr₂)-κ²N,P}] (8) was prepared by prolonged heating of phosphinohydrazine 1 with NiCp₂ in toluene. The lithiation of 3 with n-BuLi resulted in the formation of an iminophosphoranate [LiN═PiPr₂−NMe−PiPr₂] (13) (in situ), which is the product of insertion of a PiPr₂ group into the nitrogen−nitrogen bond. The hydrolysis of 13 followed by the addition of CoCl₂ gave the phosphino−iminophosphoranato complex [CoCl₂{(HN═PiPr₂−NMe−PiPr₂)-κ²N,P}] (15) according to X-ray investigation. The phosphinohydrazine 3 reacted with FeX₂ in toluene to form adducts (1:1) [FeX₂{(PiPr₂−NMe−NH−PiPr₂)-κ²P,P′}] (X = Cl (9), Br (10)), while CoCl₂ gave the complex salt [{Co(PiPr₂−NMe−NH−PiPr₂)-κ²P,P′}₂(μ-Cl)₃][CoCl₃(THF)] (11). A THF solution of complex 11 shows thermochromic behavior.