Noninnocent ligands: heteroleptic nickel complexes with α-diimine and 1,2-diketone derivatives

Hong Yang; Yanxia Zhao; Bin Liu; Ji-Hu Su; Igor L Fedushkin; Biao Wu; Xiao-Juan Yang

doi:10.1039/c7dt00455a

Noninnocent ligands: heteroleptic nickel complexes with α-diimine and 1,2-diketone derivatives

Dalton Trans. 2017 Jun 28;46(24):7857-7865. doi: 10.1039/c7dt00455a. Epub 2017 Jun 9.

Authors

Hong Yang¹, Yanxia Zhao¹, Bin Liu¹, Ji-Hu Su², Igor L Fedushkin³, Biao Wu¹, Xiao-Juan Yang¹

Affiliations

¹ Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710069, China. yangxiaojuan@nwu.edu.cn.
² Hefei National Laboratory for Physical Sciences at Microscale and Department of Modern Physics, University of Science and Technology of China, Hefei 230026, China.
³ G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Tropinina 49, 603950, Nizhny Novgorod GSP-445, Russia.

PMID: 28598473
DOI: 10.1039/c7dt00455a

Abstract

Reaction of the Ni-Ni-bonded compound [(Ni^IL˙^-)₂] (1, L = [(2,6-iPr₂C₆H₃)NC(Me)]₂) with various 1,2-diketones afforded a series of heteroleptic complexes: [LNi(PhC(O)-C(O)Ph)] (2), [LNi(PhC(O)-C(O)Me)] (3), [LNi(3,5-tBu₂C₆H₂O₂)] (4), and [(LNi){μ-η²,η²-(MeC(O)-C(O)Me)}(NiL)] (5). Furthermore, the complex [Na(Et₂O)][LNi{PhC(O)-C(O)Ph}] (6) was obtained by the reduction of 2 with 1.0 equiv. of Na metal. These complexes, which contain three potential redox-active centers, nickel and both α-diimine and 1,2-diketone ligands, were characterized by X-ray crystallography, NMR, EPR, and UV-vis-NIR spectra, magnetic susceptibility measurements, and DFT computations to elucidate their electronic structures.