Synthesis and characterization of cobalt NCN pincer complexes

A series of cobalt complexes, stabilized by a monoanionic tridentate NCN pincer ligand, was synthetized and characterized. Preparation of the paramagnetic 15 VE complex [Co(NCNCH2-Et)Br] (1) was accomplished by transmetalation of Li[2,6-(Et2NCH2)2C6H3] with CoBr2 in THF. Treatment of this air-sensitive compound with NO gas resulted in the formation of the diamagnetic Co(III) species [Co(NCNCH2-Et)(NO)Br] (2) as confirmed by X-ray diffraction. This complex features a strongly bent NO ligand (Co-N-O∠135.0°). The νNO is observed at 1609 cm-1 which is typical for a bent metal-N-O arrangement. Coordinatively unsaturated 1 could further be treated with pyridine, isocyanides, phosphines and CO to form five-coordinate 17 VE complexes. Oxidation of 1 with CuBr2 led to the formation of the Co(III) complex [Co(NCNCH2-Et)Br2]. Treatment of [Co(NCNCH2-Et)Br2] with TlBF4 as halide scavenger in acetonitrile led to the formation of the cationic octahedral complex [Co(NCNCH2-Et)(MeCN)3](BF4)2. A combination of X-ray crystallography, IR-, NMR- and EPR-spectroscopy as well as DFT/CAS-SCF calculations were used to characterize all compounds.