A β‐Diketiminato‐Based Pincer‐Type Nickel(II) Complex: Synthesis and Catalytic Performance in the Cross‐Coupling of Aryl Fluorides with Aryl Grignard Reagents
- 7 December 2018
- journal article
- research article
- Published by Wiley in European Journal of Inorganic Chemistry
- Vol. 2019 (1) , 126-133
Abstract
A β‐diketiminato‐based tridentate pincer‐type nickel(II) complex Ni‐NNP was prepared by the reaction of the nickel(II) precursor [NiCl2(2,4‐lutidine)2] with the lithiated NNP ligand, which was generated in situ by the reaction of the NNP pro‐ligand H‐NNP with nBuLi. H‐NNP was prepared by the condensation of 4‐[(2,4,6‐trimethylphenyl)amino]pent‐3‐en‐2‐one with 2‐(diphenylphosphanyl)ethylamine. Ni‐NNP was characterized spectroscopically and by X‐ray diffraction, revealing a slightly distorted square‐planar geometry around the nickel center. Density functional theory calculations indicated that the highest occupied molecular orbital in Ni‐NNP is located at higher energy than those of three other homologous nickel(II) complexes, i.e., Ni‐ONN, Ni‐ONP, and Ni‐NNN, which contain β‐aminoketonato‐ or β‐diketiminato‐based pincer‐type ligands. The electronic and steric properties of Ni‐NNP effectively facilitated the cross‐coupling of aryl fluorides with aryl Grignard reagents.Keywords
Funding Information
- KAKENHI (25410063, JP17K05805)
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