An Unsaturated Nickel(0) NHC Catalyst: Facile Preparation and Structure of Ni(0)(NHC)₂, Featuring a Reduction Process from Ni(II)(NHC)(acac)₂

A facile synthetic route to Ni(0)(NHC)2 from stable Ni(II)(acac)2 was established without common but labile Ni(0) precursors. The intermediate is a divalent mono-NHC adduct of Ni(acac)2, Ni(NHC)(acac)2. Reduction of Ni(NHC)(acac)2 in both the presence and absence of an NHC ligand gave Ni(NHC)2 in ca. 90% and 40% conversions, respectively. Ni(NHC)2, especially with bis(2,6-diisopropylphenyl)imidazolin-2-ylidene, has strong Ni−C(carbene) bonds and remarkable anagostic Ni−H(methyl) interactions, stabilizing its 14e unsaturated structure.