Synthesis, Structure and Reactivity of [(acac)AuCH(PPh 2 AuPPh 2 ) 2 CHAu(acac)], a Complex Containing the Tridentate Ligand [HC(PPh 2 ) 2 ] −

The complex [(acac)AuCH(PPh 2 AuPPh 2 ) 2 CHAu(acac)] ( 1 ) is obtained by various procedures: a) by reaction of [Ph 3 PAuCH (PPh 2 AuPPh 2 ) 2 CHAuPPh 3 ](ClO 4 ) 2 with NBu 4 [Au(acac)Cl], b) by reaction of [ClAuCH(PPh 2 AuPPh 2 ) 2 CHAuCl] with [Au(acac)PPh 3 ] or with Tl(acac) and c) by reaction of [ClAuPPh 2 CH 2 PPh 2 AuCl] with Tl(acac). The acetylacetonato ligand can act as deprotonating agent; thus, complex 1 reacts with (phosphane)gold complexes, [Au(C 6 F 5 ) 2 {(PPh 2 ) 2 ‐CH 2 )]ClO 4 , [Au(C 6 F 5 ) 3 (PPh 2 CH 2 PPh 2 )] or [Au(PPh 3 ) 2 ]ClO 4 , to give the hexanuclear complexes [(C 6 F 5 ) 2 Au{(PPh 2 ) 2 CH} AuCH(PPh 2 AuPPh 2 ) 2 CHAu{CH(PPh 2 ) 2 ) Au(C 6 F 5 ) 2 ](ClO 4 ) 2 , [(C 6 F 5 ) 3 Au(PPh 2 CHPPh 2 )AuCH (PPh 2 AuPPh 2 ) 2 CHAu‐(PPh 2 CHPPh 2 )Au(C 6 F 5 ) 3 ] or [(Ph 3 PAu) 2 C(PPh 2 AuPPh 2 ) 2 C‐(AuPPh 3 ) 2 ](ClO 4 ) 2 , respectively. The crystal structure of 1 has been established by X‐ray crystallography and displays two independent eight‐membered rings with inversion symmetry and short transannular gold‐gold contacts. The first ab initio results for a transannular Au I ‐Au I interaction are reported.