Leitl, J. and Coburger, P. and Scott, D. J. and Ziegler, C. G. P. and Hierlmeier, G. and Wolf, R. and van Leest, N. P. and de Bruin, B. and Hoerner, G. and Mueller, C. (2020) Phosphorus Analogues of [Ni(bpy)(2)]: Synthesis and Application in Carbon-Halogen Bond Activation. INORGANIC CHEMISTRY, 59 (14). pp. 9951-9961. ISSN 0020-1669, 1520-510X
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The neutral, homoleptic pyridylphosphininenickel(0) complex [Ni(2-Py-4,6-Ph (2)-PC5H2)(2)] (1) has been obtained by reaction of the formal Ni(0) source [(IPONi(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 [1(2)](BAr4F)(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, [1(2)](BAr4F)(2) exists as a dinuclear Ni(I) complex and possesses a bridging phosphinine moiety in a rare mu(2) 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 lambda(5) 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.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | CRYSTAL-STRUCTURE ANALYSIS; ELECTROCHEMICAL REDUCTION; COORDINATION CHEMISTRY; ORGANIC HALIDES; ARYL HALIDES; SPECTROSCOPIC PROPERTIES; PHOTOPHYSICAL PROPERTIES; OXIDATIVE ADDITION; GRIGNARD-REAGENTS; COMPLEXES; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 18 Mar 2021 08:04 |
| Last Modified: | 18 Mar 2021 08:04 |
| URI: | https://pred.uni-regensburg.de/id/eprint/44190 |
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