Synthesis and characterization of mononuclear amidogold(III) complexes -: Crystal structure of [Au(N2C10H7(CMe2C6H4)-6](NHC6H3Me2-2,6)][PF6] -: Oxidation of 4-methylaniline to azotoluene

Mononuclear amidogold(III) complexes [Au(C,N,N)(NRR')]-[PF6] [C,N,N = N2C10H7(CMe2C6H4)-6, where N2C10H8 = 2,2'-bipy; R H, R' = p-tolyl (5), o-xylyl (6), isobutyl (7), sec-butyl (8), R R' = Et (9)], [Au(C,N)(AcO)(NHC6H4NO2-4)] (10) [C,N = NC5H4(CH2C6H4)-2, where NC5H5 = py] and [Au(N,N)(NHC6H4NO2-4)(2)][PF6] (11) (N,N = 2,2'-bipy), have been synthesized in fairly good yields by reaction of the hydroxo, methoxo, or acetato complexes 1-4 [[Au(C,N,N)-(OR)][PF6] [R = H (1), Me (2)], [Au(C,N)(ACO)(2)] (3), [Au-(N,N)(OH)(2)][PF6] (4)) with amines. The structure of [Au(C,N,N)(NHC6H3Me2-2,6)][PF6] (6) has been determined by X-ray diffraction. Reaction of the hydroxo complex 4 with NH2C6H4Me-4 gives metallic gold, the protonated ligand [N,NH][PF6] and organic products, the main one being azotoluene. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).