Synthesis and characterization of heteromultinuclear Ni/M clusters (M = Fe, Ru, W) including a paramagnetic (NHC)Ni-WCp*(CO)₃ heterobinuclear complex.

ABSTRACT: A diverse range of heteromultinuclear Ni^I/[M_CO] clusters (M_CO = CpFe(CO)₂, CpRu(CO)₂, Cp*W(CO)₃) supported by a N-heterocyclic carbene ligand have been synthesized by reacting the Ni^I precursor, [IPrNi(μ-Cl)]₂, with [M_CO]^- reagents under various conditions. Clusters with Ni₂Fe₂, NiFe₂, Ni₂Ru, Ni₂Ru₂, NiRu₂, and Ni₂W, and NiW cores were all characterized using NMR and IR spectroscopies and X-ray crystallography. The Ni^I-containing paramagnetic heterobinuclear species, IPrNi-Wp* (7), was further characterized by EPR spectroscopy and DFT calculations. Notably, unlike previously studied (NHC)Cu^I-[M_CO] derivatives, complex 7 was found to coordinate Lewis bases like 3-chloropyridine to produce (IPr)(^3-Clpy)NiWp* (9). Complex 9 further underwent thermolytic C-Cl activation, proposed to involve NHC-free [(^3-Clpy)Ni(μ-Wp*)]₂ (10), to provide the C-arylated N-heterocyclic carbene product, [IPr(py-3-yl)]⁺[Cp*WCl₂(CO)₂]^- (11).

SUBMITTER: Yu HC 

PROVIDER: S-EPMC9674107 | biostudies-literature | 2021 Jul

REPOSITORIES: biostudies-literature