Phosphorus Analogues of [Ni(bpy) 2] : Synthesis and Application in Carbon–Halogen Bond Activation

Titelangaben

Leitl, Julia ; Coburger, Peter ; Scott, Daniel J. ; Ziegler, C. G. P. ; Hierlmeier, Gabriele ; Wolf, Robert ; van Leest, Nicolaas P. ; de Bruin, Bas ; Hörner, Gerald ; Müller, Christian:
Phosphorus Analogues of [Ni(bpy) 2] : Synthesis and Application in Carbon–Halogen Bond Activation.
In: Inorganic Chemistry. Bd. 59 (2020) Heft 14 . - S. 9951-9961.
ISSN 1520-510X
DOI: https://doi.org/10.1021/acs.inorgchem.0c01115

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Abstract

The neutral, homoleptic pyridylphosphininenickel(0) complex [Ni(2-Py-4,6-Ph2-PC5H2)2] (1) has been obtained by reaction of the formal Ni(0) source [(IPr)Ni(H2C═CHSiMe3)2] with 2 equiv of 2-(2'-pyridyl)-4,6-diphenylphosphinine (L). Compound 1 can be oxidized both electrochemically and through the use of ferrocenium salts, to afford the corresponding Ni(I) complexes [1]BF4, [1(THF)]PF6, and [12](BArF4)2. The structures of these salts reveal an interesting dependence on the nature of the anion. While [1]BF4 and [1(THF)]PF6 show trigonal-bipyramidal coordination of Ni in the solid state, [12](BArF4)2 exists as a dinuclear Ni(I) complex and possesses a bridging phosphinine moiety in a rare μ2 mode. Reactions of 1 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 1 with bromobenzene affords the λ5 phosphinine 2 and the bipyramidal Ni(I) complex [1]Br, whereas a more unconventional oxidation product 3 is formed from the reaction of 1 and iodobenzene.