Nickel complexes of a bis(benzimidazolin-2-ylidene)pyridine pincer ligand with four- and five-coordinate geometries
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The four- and five-coordinate complexes [(CNC)NiX2] (X = Cl, Br, I), [(CNC)NiX]PF6 (X = Cl,Br) and [(CNC)NiCl]ClH2O have been isolated, where CNC is the bis(N-butylbenzimidazolin-2-ylidene)-2,6-pyridine pincer ligand. A five-coordinate geometry is rare for this class of complex.Where amenable, the complexes have been structurally characterised by single crystal X-raydiffraction studies and in solution by NMR, UV-vis and MS studies. The five-coordinate dibromocomplex [(CNC)NiBr2] is readily prepared on the gram-scale from the benzimidazolium saltprecursor and Ni(OAc)24H2O in DMSO without the exclusion of air. Halide exchange and saltmetathesis reactions using [(CNC)NiBr2] afford the other four- and five-coordinate complexes.[(CNC)NiBr2] displays very low solubility, and upon dissolution affords solutions of the fourcoordinate[(CNC)NiBr]+. Factors that influence the formation of four- or five-coordinatecomplexes with this ligand class are discussed.
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Synthesis, Solid-state Structures, Solution Behaviour and Catalysis Studies of Nickel Complexes of Bis(benzimidazolin-2-ylidene)pyridine Pincer LigandsMcGee, Karen; Travers, Guy; Skelton, B.; Massi, Massimiliano; Payne, A.; Brown, David (2012)N-Heterocyclic carbene–nickel complexes with five- and four-coordinate geometries [(CNC)NiBr2] and [(CNC)NiBr]X (X = PF6 or BPh4) have been prepared with the pincer ligands 2,6-bis(N-octylbenzimidazolin-2-ylidene)pyridine ...
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