Gold(I) and Silver(I)/Gold(I) Complexes Derived from C6Me4(C⋮CH)2-1,2

C 6 Me 4 (C⋮CH) 2 -1,2 [Ar(C⋮CH) 2 ] reacts with PPN[Au(acac) 2 ] (acac = acetylacetonato, PPN = (Ph 3 P) 2 N) (2:1) or with [AuCl(SMe 2 )] and NEt 3 (1:2:2) to give PPN[Au{C⋮CArC⋮CH} 2 ] ( 1 ) or [Au 2 {μ-Ar(C⋮C) 2 })] n ( 2 ), respectively. Dinuclear complexes of general formula [Au 2 L 2 {μ-Ar(C⋮C) 2 }] can be obtained by reacting 2 with the appropriate ligand L (1:2) [L = t BuNC ( 3 ), PMe 3 ( 4 ), PTo 3 ( 5, To = C 6 H 4 Me-4)] or L 2 (1:1) (L 2 = Ph 2 P(CH 2 ) n PPh 2, n = 4 ( 6 ), 6 ( 7 )]. The analogous complexes [(AuNHEt 2 ) 2 {μ-Ar(C⋮C) 2 }] ( 8 ) and [{AuC(NH t Bu)(NEt 2 )} 2 {μ-Ar(C⋮C) 2 }] ( 9 ) result from the reactions of Ar(C⋮CH) 2 with PPN[AuCl 2 ] and NHEt 2 (1:2:4) or 3 with an excess of NHEt 2, respectively. The reaction of 5 with AgClO 4 (2:1) gives the heteropentanuclear “AgAu 4 ” complex [Ag{(AuPTo 3 ) 2 {μ-Ar(C⋮C) 2 }} 2 ]ClO 4 ( 10 ). The X-ray crystal structures of 3, 7, 9 ·1/3CHCl 3, and 10 ·2CHCl 3 have been determined.