Mononuclear (Pd,Pt), Heterodinuclear (Pdag,PtAg), and Tetranuclear (Pd_2Ag_2, Pt_2Ag_2) 1,1-Ethylenedithiolato Complexes

摘要

1p;&-5q;IThe reactions of [Tlz{S2C=C{C(O)Meh}]n with [MCI2L2] (1:1) or with [MClz(NCPh)2] and PPh3 (I: I :2) give complexes [M{1J2_S2C=C{C(O)Meh}L2] [M = Pt, L2 = 1 ;5-cyclooctadiene (cod) {I); L2 = bpy, M = Pd (2a), Pt (2b), L = PPh3, M = Pd (3a), Pt (3b)] whereas with MClz and QC1 (2:1 :2) anionic derivatives Q2[M{1J2-S2C=C{C(O)Mehh] fM = Pd, Q = NMe4 (4a), Ph3P=N=PPh3 (PPN) (4a'), M = Pt, Q = NMe4 (4b)] are produced. Complexes I and 3 react with AgCIO4 (1:1) to give tetranuclear complexes {{MLz}2Ag2- {ji2,1J2-(S,S')-{S2C=C{C(O)Me}Z}Z}](CIO4n fL = PPh3, M = Pd (5a), Pt (5b), L2 = cod, M = Pt (5b')], while the reactions of 3 with AgCIO4and PPh3 (1:1:2) give dinuclear [{M(PPh3)z}{Ag(PPh3)z}{ji2,1J2_(S;S')-{S2C= C{C(O)Me}z}}]C104 [M = Pd(6a), Pt (6b)]. The crystal structures of3a, 3b, 4a, and two crystal forms of5b have been determined. The two crystal forms of5b display two {Pt(PPh3)2}{ji2,1J2_(S,S')-'{S2C=C{C(O)Me}2h} moieties bridging two Ag(I) centers.