Three-Electron Nickel(I)/Nickel(0) Half-Bond

An (N-heterocyclic carbene)nickel(I) cation precursor reacts with the corresponding nickel(0) complex to form a dinickel(I,0) monocation. The Ni···Ni distance in this cation is 0.93 Å shorter than in the analogous dinickel(0) complex. Although the solid-state structure shows equivalent Ni centers, density functional theory calculations indicate significant electronic localization. Reactions with CO and NO form mononuclear carbonyl and nitrosyl complexes. Oxidative addition of an aryl bromide results in C-arylation of the carbene ligands.