1p;&-5q;1The reactions of [Tl-2{S2C=C{C(O)Me}(2)}](n) with [MCl2L2] (1:1) or with [MCl2(NCPh)(2)] and PPh3 (1:1:2) give complexes [M{eta (2)-S2C=C{C(O)Me}(2)}L-2] [M = Pt, L-2 = 1,5-cyclooctadiene (cod) (1); L-2 = bpy, M = Pd (2a), Pt (2b), L = PPh3, M = Pd (3a), Pt (3b)] whereas with MCl2 and QCl (2:1:2) anionic derivatives Q(2)[M{eta (2)-S2C=C(O)Me}(2)}(2)] [M = Pd, Q = NMe4 (4a), Ph3P=N=PPh3 (PPN) (4a '), M = Pt, Q = NMe4 (4b)] are produced. Complexes 1 and 3 react with AgClO4 (1:1) to give tetranuclear complexes [{ML2}(2)Ag-2-{mu (2),eta (2)-(S,S ')-{S2C=C{C(O)Me}(2)}(2)}](ClO4)(2) [L = PPh3, M = Pd (5a), Pt (5b), L-2 = cod, M = Pt (5b ')], while the reactions of 3 with AgClO4 and PPh3 (1:1:2) give dinuclear [{M(PPh3)(2)}{Ag(PPH3)(2)}{mu (2)-eta (2)-(S,S ')-{S2C=C{C(O)Me}(2)}}]ClO4 [M = Pd (6a), Pt (6b)]. The crystal structures of 3a, 3b, 4a, and two crystal froms of 5b have been determined. The two crystal forms of 5b display two {Pt(PPh3)(2)}{mu (2)-eta (2)-(S,S ')-{S2C=C{C(O)Me}(2)}(2)} moieties bridging two Ag(I) centers.