Leitl J, Coburger P, Scott D J, Ziegler C G P, Hierlmeier G, Wolf R, van Leest N P, de Bruin B, Hörner G, Müller C
Institute of Inorganic Chemistry, Universität Regensburg, 93040 Regensburg, Germany.
van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands.
Inorg Chem. 2020 Jul 20;59(14):9951-9961. doi: 10.1021/acs.inorgchem.0c01115. Epub 2020 Jul 2.
The neutral, homoleptic pyridylphosphininenickel(0) complex [Ni(2-Py-4,6-Ph-PCH)] () has been obtained by reaction of the formal Ni(0) source [(IPr)Ni(HC═CHSiMe)] with 2 equiv of 2-(2'-pyridyl)-4,6-diphenylphosphinine (). Compound can be oxidized both electrochemically and through the use of ferrocenium salts, to afford the corresponding Ni(I) complexes []BF, [(THF)]PF, and . The structures of these salts reveal an interesting dependence on the nature of the anion. While []BF and [(THF)]PF show trigonal-bipyramidal coordination of Ni in the solid state, exists as a dinuclear Ni(I) complex and possesses a bridging phosphinine moiety in a rare μ mode. Reactions of with halobenzenes highlight the noninnocent behavior of the aromatic phosphinine ligand, leading to the formation of oxidized Ni complexes but not to classical oxidative addition products. The reaction of with bromobenzene affords the λ phosphinine and the bipyramidal Ni(I) complex []Br, whereas a more unconventional oxidation product is formed from the reaction of and iodobenzene.
中性、均配型吡啶基膦镍(0)配合物Ni(2-Py-4,6-Ph-PCH)是通过形式上的Ni(0)源[(IPr)Ni(HC═CHSiMe)]与2当量的2-(2'-吡啶基)-4,6-二苯基膦()反应得到的。化合物可以通过电化学方法以及使用二茂铁盐进行氧化，得到相应的Ni(I)配合物[]BF、[(THF)]PF和。这些盐的结构显示出对阴离子性质的有趣依赖性。虽然[]BF和[(THF)]PF在固态中显示出Ni的三角双锥配位，但以双核Ni(I)配合物形式存在，并且在罕见的μ模式下具有桥连膦部分。与卤代苯的反应突出了芳基膦配体的非无辜行为，导致形成氧化的Ni配合物，而不是经典的氧化加成产物。与溴苯的反应得到λ膦 和双锥Ni(I)配合物[]Br，而与碘苯的反应形成了一种更非常规的氧化产物 。
