Nickel Phosphanido Hydride Complex: An Intermediate in the Hydrophosphination of Unactivated Alkenes by Primary Phosphine

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• 作者：Yulia S. Ganushevich ; Vasily A. Miluykov ; Fedor M. Polyancev ; Shamil K. Latypov ; Peter L枚nnecke ; Evamarie Hey-Hawkins ; Dmitry G. Yakhvarov ; Oleg G. Sinyashin
• 刊名：Organometallics
• 出版年：2013
• 出版时间：July 22, 2013
• 年：2013
• 卷：32
• 期：14
• 页码：3914-3919
• 全文大小：317K
• 年卷期：v.32,no.14(July 22, 2013)
• ISSN：1520-6041

文摘

Heating of a mixture of [Ni(CH₂鈺怌H₂)(dtbpe)] (dtbpe = 1,2-bis(di-tert-butylphosphino)ethane) and 2,6-dimesitylphenylphosphine (DmpPH₂) in toluene gives the secondary phosphine (Dmp)P(Et)(H) (1) as the main product. However, thermolysis of [Ni(CH₃)₂(dtbpe)] in the presence of DmpPH₂ in toluene leads to the mononuclear nickel phosphanido hydride complex [NiH{P(Dmp)(H)}(dtbpe)] (2), the product of an oxidative addition of a primary phosphine to nickel(0). The structure of complex 2 was confirmed by single-crystal X-ray diffraction and DNMR studies. The mutual exchange of tautomers in which the Ni鈥揌 and P鈥揌 hydrogen atoms interchange as well as the position of the hydrido and the phosphanido ligand occurs in solution. The stoichiometric reaction of 2 with 1-hexene proceeds regiospecifically to form the secondary phosphine (Dmp)P(Hex)(H) (3).