Synthesis and Characterisation of Low-Coordinate Transition-Metal Complexes Stabilised by Sterically Demanding Carbazolido Ligands

The synthesis and characterisation of the homoleptic transition-metal complexes (1,8-Ph-2-3,6-Me2C12H4N)(2)M (M = Cr, I; M = Mn, 2; M = Fe, 3; M = Co, 4) are described, Formally two-coordinate, the solid-state structures of 2 and 3 reveal near-linear N-M-N geometries and significant bending of the flanking phenyl groups towards the metal centres. Solid-state magnetic measurements reveal high spin metal centres in 1-4; computational calculations for the model complexes M(1,8-Ph2C12H6N)(2) (M = Cr-Co) confirm the presence of high-spin configurations within these bis-carbazolido compounds and an orbital ordering of delta < pi < sigma for these systems. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)