CP-ASTERISK-IR(DAB) AB=1,4-BIS(2,6-DIMETHYLPHENYL)-1,4-DIAZABUTADIENE) - A COORDINATIVELY UNSATURATED 6-PI-ELECTRON METALLAHETEROAROMATIC COMPOUND

,4-Bis(2,6-dimethylphenyl)-1,4-diaza-1,3-butadiene (dab) forms the str ucturally characterized iridium(III) complex [CpIrCl(dab)](PF6): C28H 35CIF6IrN2P, orthorhombic, space group Pnma, a = 16.187(2) Angstrom, b = 15.823(2) Angstrom, c = 11.677(1) Angstrom, V = 2990.8(6) Angstrom( 3), Z = 4, and R = 0.0588. On reaction with NaBH3CN this compound does not form an iridium(III) hydride but the coordinatively unsaturated r educed product CpIr(dab): C28H35IrN2, monoclinic, space group P2(1)/n , a = 8.484(2) Angstrom, b = 14.535(3) Angstrom, c = 20.956(4) Angstro m, beta = 98.88(3)degrees, V = 2553.2(9) Angstrom(3), Z = 4, and R = 0 .0586. The inverted relation d(CC) (=1.334(15) Angstrom) (d(CN)) (=1.3 79(13) and 1.366(14) Angstrom) in the dab ligand of CpIr(dab) suggest s that the reduction has occurred primarily at that ligand to form an ene-1,2-diamido/iridium(III) moiety or, alternatively, a six-pi-electr on metallaheteroaromatic system. Ab initio pseudopotential calculation s of model complexes [CpIr(HNCHCHNH)](0/2+) support this description o f the bonding.