Substitution and reduction reactions of halogenated dinuclear gold ylide complexes with anionic sulfur reagents. The molecular structures of {Au II[μ-(CH 2) 2PPh 2]} 2((DTP) 2 ( 1), {Au II[μ-(CH 2) 2PMe 2]} 2(MTP) 2 ( 3), anti-{[Au IIIBr(MTP)[μ-(CH 2) 2PPh 2]}· C 6H 6 ( 4), {Au II[μ-(CH 2) 2PPh 2]} 2(MTP)Br ( 5) and {Au 2III(μ-CH 2)-[μ-(CH 2) 2PPh

Abstract

Substitution reactions and reductions with the salts of potentially bidentate ligands, Li(MTP) (MTP = methylenediphenylthiophosphinate) and K(DTP) (DTP = diphenyldithiosphosphinate), have been carried out using {Au IIIBr 2[μ-(CH 2) 2PR 2]} 2 (RMe, P {Au II[μ-(CH 2) 2PPH 2]} 2Br 2, and {Au III 2(μ-CH 2)[μ-(CH 2) 2[μ-(CH 2) 2PPh 2] 2}Br 2 as starting materials. Metathesis products are f without evidence of formation of mixed-valent Au 1/Au III metallacycles from the Au II starting materials and metal-metal bonded Au II products are observed fr the dinuclear Au III halides. The molecular structures of {Au[μ-(CH 2) 2PPh 2]} 2(DTP) 2 ( 1), {Au[μ-(CH 2) 2PMe 2]} 2(MTP) 2 ( 3), anti-{[AuBr(MTP)[μ-CH 2) 2PPh 2]} 2·C 6H 6 ( 4), {Au[μ-(CH 2) 2PPh 2]} 2(MTP)Br ( 5) {Au 2(μ-CH 2)[μ-(CH 2) 2PPh 2] 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) A ̊ , β=91.75(2)° and V=4938(3) A ̊ 3 . Complex 3 crystallizes in the triclinic space group P 1 with Z=2, a=9.215(2), b=13.878(3), c=15.120(3) A ̊ , a=81.74(2), β=76.31(2), γ=89.29°(2)° and V=1858.7(7) A ̊ 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) A ̊ , β=91.90(1)° and V=3174.9(8) A ̊ 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 A ̊ and V=7898(4) A ̊ 3 . Complex 7 crystallizes in the triclinic space group P 1 with Z=2, a=12.975(2), b=13.551(2), c=14.533(3) A ̊ , α=85.14(1)°, β-84.37(1), γ=81.81(1)° and V=2510.4° A ̊ 3 .