Stabilization of a two-coordinate mononuclear cobalt(0) compound.

Abstract

Compound (Me2 -cAAC:)2 Co(0) (2; Me2 -cAAC:=cyclic (alkyl) amino carbene; :C(CH2 )(CMe2 )2 N-2,6-iPr2 C6 H3 ) was synthesized by the reduction of the precursor (Me2 -cAAC:)2 Co(I) Cl (1) with KC8 in THF. The cyclic voltammogram of 1 exhibited one-electron reduction, which suggests that synthesis of a bent 2-metallaallene (2) from 1 should be possible. Compound 2 contains one cobalt atom in the formal oxidation state zero, which is stabilized by two Me2 -cAAC: ligands. Bond lengths from X-ray diffraction are 1.871(2) and 1.877(2) Å with a C-Co-C bond angle of 170.12(8)°. The EPR spectrum of 2 exhibited a broad resonance attributed to the unique quasi-linear structure, which favors near degeneracy and gives rise to very rapid relaxation conditions. The cAACCo bond in 2 can be considered as a typical Dewar-Chatt-Duncanson type of bonding, which in turn retains 2.5 electron pairs on the Co atom as nonbonding electrons.