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

作者：Ganushevich Yulia S; Miluykov Vasily A^*; Polyancev Fedor M; Latypov Shamil K; Loennecke Peter; Hey Hawkins Evamarie; Yakhvarov Dmitry G; Sinyashin Oleg G

来源：Organometallics, 2013, 32(14): 3914-3919.

DOI：10.1021/om400408e

Heating of a mixture of [Ni(CH2=CH2)(dtbpe)] (dtbpe = 1,2-bis(di-tert-butylphosphino)ethane) and 2,6-dimesityl-phenylphosphine (DmpPH(2)) 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 DmpPH(2) 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-H and P-H 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).

• 出版日期2013-7-22