Stabilization of a Two-Coordinate Mononuclear Cobalt(0) Compound

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Chemistry - A European Journal, 20 (37): 11646--11649 (2014)
DOI: 10.1002/chem.201403525


Compd. (Me2-cAAC:)2Co0 (2; Me2-cAAC: = cyclic (alkyl)amino carbene; :C(CH2)(CMe2)2N-2,6-iPr2C6H3) was synthesized by the redn. of the precursor (Me2-cAAC:)2CoICl (1) with KC8 in THF. The cyclic voltammogram of 1 exhibited one-electron redn., which suggests that synthesis of a bent 2-metallaallene (2) from 1 should be possible. Compd. 2 contains one cobalt atom in the formal oxidn. state zero, which is stabilized by two Me2-cAAC: ligands. Bond lengths from x-ray diffraction are 1.871(2) and 1.877(2) \AA 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. on SciFinder(R)



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