Synthesis of Low-Valent Nickel Complexes in Aqueous Media, Mechanistic Insights, and Selected Applications
作者:Illán Morales-Becerril、Marcos Flores-Álamo、Adrián Tlahuext-Aca、Alma Arévalo、Juventino J. García
DOI:10.1021/om500767p
日期:2014.12.8
The synthesis of nickel(0) complexes usually requires the employment of strong reducing agents, including powerful hydride donors such as LiHBEt3, LiAlH4, and DIBAL-H. Herein, we have reduced the Ni(II) complex [(dippe)NiCl2] (1a) at room temperature by using KOH in aqueous media to yield the low-valent complex [Ni(dippe)2] (4a) as the main product, along with the formation of dippeO2. In order to
镍(0)配合物的合成通常需要使用强还原剂,包括强力氢化物供体,例如LiHBEt 3,LiAlH 4和DIBAL-H。在此,我们通过在水性介质中使用KOH在室温下还原了Ni(II)络合物[(dippe)NiCl 2 ](1a),以低价络合物[Ni(dippe)2 ](4a)为主要成分产物,并形成dippeO 2。为了深入了解反应机理,分离了一系列中间体,并在不同的反应阶段进行了表征。结果,Ni(II)羟基桥(2b)和氢化物(3b))复合物被确定为关键中间体。此外,还研究了在镍介导的过程中使用水作为氢源并将其成功应用于选定的有机底物的加氢脱氟,加氢脱硫和加氢。