Migratory Insertion of the R2P Group into a Nitrogen−Nitrogen Bond − A Novel Type of Rearrangement in Phosphorus−Nitrogen Ligand Chemistry. 3. The Rearrangement of Trip

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• 作者：Vyacheslav V. Sushev ; Natalia V. Belina ; Georgy K. Fukin ; Yuriy A. Kurskiy ; Alexander N. Kornev ; Gleb A. Abakumov
• 刊名：Inorganic Chemistry
• 出版年：2008
• 出版时间：April 7, 2008
• 年：2008
• 卷：47
• 期：7
• 页码：2608 - 2612
• 全文大小：346K
• 年卷期：v.47,no.7(April 7, 2008)
• ISSN：1520-510X

文摘

Hydrazine dihydrochloride reacts with 3 equiv of Ph₂PCl in tetrahydrofuran in the presence of triethylamine to give tris(diphenylphosphino)hydrazine (1) in 70% yield. Each nitrogen atom in 1 has a trigonal-planar environment according to X-ray analysis. Thermolysis of 1 at 130 °C results in the formation of two products: bis(diphenylphosphino)amine and octaphenylcyclotetraphosphazene. The interaction of free ligand 1 with NiBr₂ affords a simple adduct [(Ph₂P)₂N−NH−PPh₂]NiBr₂, while its anionic (hydrazide) form undergoes rearrangement in a coordination sphere of divalent cobalt and nickel involving migratory insertion of the Ph₂P group into a nitrogen−nitrogen bond. The reaction of 1 with cobalt bis(trimethylsilyl)amide, [(Me₃Si)₂N]₂Co, yields the complex of phosphazenide-type (Me₃Si)₂N−Co[(Ph₂PN)₂PPh₂] (2) in 86% yield. A similar reaction of 1 with nikelocene proceeds with substitution of one Cp ring to form durable 18-electron complex CpNi[(Ph₂PN)₂PPh₂] (3).