Substitution and reduction reactions of halogenated dinuclear gold ylide complexes with anionic sulfur reagents. The molecular structures of {Au-II[mu-(CH2)(2)PPh2]}(2)(DTP)(2) (1), {Au-II[mu-(CH2)(2)PMe2]}(2)(MTP)(2) (3), anti-{[Au-III;Br(MTP)][mu-(CH2)(2)PPh2]}(2).C6H6 (4), {Au-II[mu-(CH2)(2)PPh2]}(2)(MTP)Br (5) and {Au-III;(2)(mu-CH2)[mu-(CH2)(2)PPh2](2)}(DTP)(2) (7), MTP=[CH2P(S)Ph-2](-), DTP=[S2PPh2](-)

Substitution reactions and reductions with the salts of potentially bidentate ligands, Li(MTP) (MTP = methylenediphenylthiophosphinate) and K(DTP) (DTP = diphenyldithiophosphinate), have been carried out using {(AuBr2)-Br-III[mu-(CH2)(2)PR2]}(2) (R = Me, Ph), (Au-II[mu-(CH2)(2)PPh2]}(2)Br-2, and (Au-2(III)(mu-CH2)[mu-(CH2)(2)PPh2](2)}Br-2 as starting materials. Metathesis products are formed without evidence of formation of mixed-valent Au-I/Au-III metallacycles from the Au-II starting materials and metal-metal bonded Au-II products are observed from the dinuclear Au-III halides. The molecular structures of {Au[mu-(CH2)(2)PPh2]}(2)(DTP)(2) (1), {Au[mu-(CH2)(2)PMe2]}(2)(MTP)(2) (3), anti-{[AuBr(MTP)[mu-(CH2)(2)PPh2]}(2).C6H6 (4), {Au[mu-(CH2)(2)PPh2]}(2)(MTP)Br (5) and {Au-2(mu-CH2)[mu-(CH2)(2)PPh2](2)}(DTP)(2) (7) have been obtained by X-ray crystallography. These ligands both bond to different gold centers through only one functional group. A discussion is presented of the amplified structural trans influence as it relates to these compounds. Complex 1 crystallizes in the monoclinic space group P2(1)/c with Z=4, a=19.335(5), b=9.073(3), c=28.160(9) Angstrom, beta=91.75(2)degrees and V=4938(3) Angstrom(3). Complex 3 crystallizes in the triclinic space group P (1) over bar with Z=2, a=9.215(2), b=13.878(3), c=15.120(3) Angstrom, alpha=81.74(2), beta=76.31(2), gamma=89.29(2)degrees and V=1858.7(7) Angstrom(3). Complex 4 crystallizes in the monoclinic space group P2(1)/n with Z=2, a=13.189(2), b=16.742(3), c=14.386(2) Angstrom, beta=91.90(1)degrees and V=3174.9(8) Angstrom(3). Complex 5 crystallizes in the orthorhombic space group Pbca with Z=8, a=17.787(4), b=18.647(4), c=23.814(9) Angstrom and V=7898(4) Angstrom(3). Complex 7 crystallizes in the triclinic space group P (1) over bar with Z=2, a=12.975(2), b=13.551(2), c=14.533(3) Angstrom, alpha=85.14(1)degrees, beta=84.37(1), gamma=81.81(1)degrees and V=2510.4(8) Angstrom(3). (C) 1997 Elsevier Science S.A.