Synthesis and Characterization of Mononuclear Amidogold( III ) Complexes − Crystal Structure of [Au(N 2 C 10 H 7 (CMe 2 C 6 H 4 )‐6](NHC 6 H 3 Me 2 ‐2,6)][PF 6 ] − Oxidation of 4‐Methylaniline to Azotoluene

Mononuclear amidogold( III ) complexes [Au(C,N,N)(NRR′)][PF 6 ] [C,N,N = N 2 C 10 H 7 (CMe 2 C 6 H 4 )‐6, where N 2 C 10 H 8 = 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)(NHC 6 H 4 NO 2 ‐4)] ( 10 ) [C,N = NC 5 H 4 (CH 2 C 6 H 4 )‐2, where NC 5 H 5 = py] and [Au(N,N)(NHC 6 H 4 NO 2 ‐4) 2 ][PF 6 ] ( 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)][PF 6 ] [R = H ( 1 ), Me ( 2 )], [Au(C,N)(AcO) 2 ] ( 3 ), [Au(N,N)(OH) 2 ][PF 6 ] ( 4 )} with amines. The structure of [Au(C,N,N)(NHC 6 H 3 Me 2 ‐2,6)][PF 6 ] ( 6 ) has been determined by X‐ray diffraction. Reaction of the hydroxo complex 4 with NH 2 C 6 H 4 Me‐4 gives metallic gold, the protonated ligand [N,NH][PF 6 ] and organic products, the main one being azotoluene. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)