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• 作者：Alexander N. Kornev ; Vyacheslav V. Sushev ; Yulia S. Panova ; Natalia V. Belina ; Olga V. Lukoyanova ; Georgy K. Fukin ; Sergey Y. Ketkov ; Gleb A. Abakumov ; Peter L枚nnecke ; Evamarie Hey-Hawkins
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：January 16, 2012
• 年：2012
• 卷：51
• 期：2
• 页码：874-881
• 全文大小：502K
• 年卷期：v.51,no.2(January 16, 2012)
• ISSN：1520-510X

文摘

Reactions of diphosphinohydrazines R鈥揘H鈥揘(PPh₂)₂ (R = tBu (1), Ph₂P (3)) with some metalation reagents (Co[N(SiMe₃)₂]₂, LiN(SiMe₃)₂, La[N(SiMe₃)₂]₃, nBuLi, MeLi) were performed. Compound 1 was synthesized by the reaction of Ph₂PCl with tert-butylhydrazine hydrochloride in 83% yield. This compound reveals temperature-dependent ³¹P NMR spectra due to hindered rotation about the P鈥揘 bonds. Complicated redox reaction of 1 with Co[N(SiMe₃)₂]₂ proceeds with cleavage of the P鈥揘 and N鈥揘 bonds to form a binuclear cobalt complex [Co{HN(PPh₂)₂-魏²P,P鈥瞹₂(渭-PPh₂)]₂ (2) demonstrating a short Co路路路Co distance of 2.3857(5) 脜, which implies a formal double bond between the Co atoms. Strong nucleophiles (nBuLi, MeLi) cause fragmentation of the molecules 1 and 3, while reactions of 3 with lithium and lanthanum silylamides give products of the NNP 鈫?NPN rearrangement [Li{Ph₂P(NPPh₂)₂-魏²N,N鈥瞹(THF)₂] (4) and [La{Ph₂P(NPPh₂)₂-魏²N,N鈥瞹{N(SiMe₃)₂}₂] (5), respectively. These complexes represent the first examples of a 魏²N,N鈥?bonding mode for the triphosphazenide ligand [(Ph₂PN)₂PPh₂]^{鈭?/sup>. DFT calculations showed large energy gain (52.1 kcal/mol) of the [NNP]鈭?/sup> to [NPN]鈭?/sup> anion rearrangement.}