Coordination Compounds of Coinage Metals with Vinylidenebis(diphenyl‐phosphane) and Its Disulfide and Their Reactivity towards Nucleophiles

Vinylidenebis(diphenylphosphane) reacts with gold(I) or gold(III) compounds to give dinuclear {[{Au(C 6 F 5 )] 2 [(PPh 2 ) 2 CCH 2 {] or [Au{PPh 2 C(CH 2 )Ph 2 P)] 2 (ClO 4 ) 2 ] or mononuclear complexes ([Au(C 6 F 5 ) 3 (PPh 2 C(CH 2 )Ph 2 P)]}, respectively. The latter reacts with gold(I) or silver(I) compounds to afford dinuclear [[Au(C 6 F 5 ) 3 [PPh 2 C(CH 2 )Ph 2 P}AuX], XCl or C 6 F 5 ) or trinuclear species {[{Au(C 6 F 5 ) 3 {PPh 2 C(CH 2 )Ph 2 P{] 2 M]ClO 4 , MAu or Ag}. No addition of nucleophiles to the CC double bond is observed in these complexes, which contain the diphosphane acting as bridging or monodentate ligand. (SPPh 2 ) 2 CCH 2 reacts with AgClO 4 to give [Ag{SPPh 2 C(CH 2 )Ph 2 PS}] 2 ‐(ClO 4 ) 2 or[Ag[PPh 2 C(CH 2 )Ph 2 P] 2 ]ClO 4 . The crystal structure of [Au(C 6 F 5 ) 3 {PPh 2 C(CH 2 )Ph 2 P}Au(C 6 F 5 )] has been established by X‐ray crystallography, and confirms the expected square planar and linear geometry for the Au 111 and Au 1 centres, respectively.