Monomeric Three-Coordinate N-Heterocyclic Carbene Nickel(I) Complexes: Synthesis, Structures, and Catalytic Applications in Cross-Coupling Reactions

Abstract

A series of three-coordinate monovalent nickel halide complexes bearing N-heterocyclic carbene (NHC) ligands, i.e., NiCl(IPr)(L) [L = pyridine, P(OPh)3, bis(diphenylphosphino)butane (dppb), IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene], NiX(IMes)(PPh3) (X = Cl and Br, IMes = 1,3-bis(mesityl)imidazol-2-ylidene), were prepared. The complexes were identified using NMR spectroscopy, superconducting quantum interference device (SQUID), and X-ray crystallography. Additionally, ESR spectra of NiCl(IPr)(pyridine) were taken in toluene. These complexes had three-coordinate Y-shaped geometries in both the solid and solution states. The compounds containing IPr showed equilibrium between the monomeric and dimeric forms, with liberation of ligands. Addition of 1,2-bis(diphenylphosphino)ethane and 1,3-bis(diphenylphosphino)propane to the dinickel(I) IPr complex instead of dppb resulted in heterolytic cleavage to nickel(0) and nickel(II) species. Catalysis of Suzuki cross-coupling and Buchwald–Hartwig amination of aryl bromide using the complexes was investigated. The efficiencies in the amination of aryl bromide depended strongly on the additional donor ligands.