Synthesis and characterization of heteromultinuclear Ni/M clusters (M = Fe, Ru, W) including a paramagnetic (NHC)Ni-WCp*(CO) heterobinuclear complex.

A diverse range of heteromultinuclear Ni/[M] clusters (M = CpFe(CO), CpRu(CO), Cp*W(CO)) supported by a N-heterocyclic carbene ligand have been synthesized by reacting the Ni precursor, [IPrNi(μ-Cl)], with [M] reagents under various conditions. Clusters with NiFe, NiFe, NiRu, NiRu, NiRu, and NiW, and NiW cores were all characterized using NMR and IR spectroscopies and X-ray crystallography. The Ni-containing paramagnetic heterobinuclear species, IPrNi-Wp* (), was further characterized by EPR spectroscopy and DFT calculations. Notably, unlike previously studied (NHC)Cu-[M] derivatives, complex was found to coordinate Lewis bases like 3-chloropyridine to produce (IPr)(py)NiWp* (). Complex further underwent thermolytic C-Cl activation, proposed to involve NHC-free [(py)Ni(μ-Wp*)] (), to provide the C-arylated -heterocyclic carbene product, [IPr(py-3-yl)][Cp*WCl(CO)] .