Grupo de Química Organometálica, Departamento de Química Inorgánica, Universidad de Murcia, Apdo. 4021, Murcia, 30071 Spain.
Inorg Chem. 2010 Sep 6;49(17):8099-111. doi: 10.1021/ic101188z.
The reaction of [Tl(2){mu-S,S-S(2)C=C{C(O)Me}(2)}] with [Au(C,N-C(6)H(4)CH(2)NMe(2)-2)Cl(2)] (1:1) gives [{Au(C,N-C(6)H(4)CH(2)NMe(2)-2)}{S,S-S(2)C=C{C(O)Me}(2)}] (1) which, in turn, reacts with AgClO(4) (1:1) to give [{Au(C,N-C(6)H(4)CH(2)NMe(2)-2)}{Ag(OClO(3))}{S(2)C=C{C(O)Me}(2)}] (2). Complexes [{Au(C,N-C(6)H(4)CH(2)NMe(2)-2)}{Ag(X)(PPh(3))}{S(2)C=C{C(O)Me}(2)}] [X = OClO(3) (3), ONO(2) (4)] have been obtained by reaction of 1 with PPh(3) and AgClO(4) or AgNO(3), respectively (1:1:1). Complex 3 can also be obtained by reacting 2 with PPh(3) (1:1). Complexes Pd(C,N-C(6)H(4)CH(2)NR(2)-2)(mu-Cl) (R = Me, H) react (i) with [Tl(2){S(2)C=C{C(O)Me}(2)}] and [PPN]Cl (0.5:1:1, PPN = Ph(3)P=N=PPh(3)) to form PPN[Pd(C,N-C(6)H(4)CH(2)NR(2)-2){S,S-S(2)C=C{C(O)Me}(2)}] [R = H (5a), Me (5b)], or (ii) with [Tl(2){S(2)C=C{C(O)Me}(2)}] (1:1) to form [{Pd(C,N-C(6)H(4)CH(2)NR(2)-2)}(2){mu-S,S,O-S(2)C=C{C(O)Me}(2)}] [R = H (6a), Me (6b)]. The trinuclear complexes [{Pd(C,N-C(6)H(4)CH(2)NR(2)-2)}(3){mu(3)-O,S,S,O-S(2)C=C{C(O)Me}(2)}]ClO(4) [R = H (7a), Me (7b)] can be prepared by reacting the corresponding dinuclear complex 6a or 6b with [Pd(C,N-C(6)H(4)CH(2)NR(2)-2)(NCMe)(2)]ClO(4) (1:1). The crystal structures of 1, 6b x CH(2)Cl(2), and 7b x CH(2)Cl(2) have been determined. NMR studies have been carried out to explain the solution behavior of these complexes. VT-NMR and line shape analysis for the species where R = Me (5b, 6b, 7b) have allowed the estimation of the activation parameters for these exchange processes.
[Tl(2){μ-S,S-S(2)C=C{C(O)Me}(2)}]与[Au(C,N-C(6)H(4)CH(2)NMe(2)-2)Cl(2)]（1:1）反应得到[{Au(C,N-C(6)H(4)CH(2)NMe(2)-2)}{S,S-S(2)C=C{C(O)Me}(2)}]（1），它又与 AgClO(4)（1:1）反应生成[{Au(C,N-C(6)H(4)CH(2)NMe(2)-2)}{Ag(OClO(3))}{S(2)C=C{C(O)Me}(2)}]（2）。通过将 1 与 PPh(3)和 AgClO(4)或 AgNO(3)分别反应（1:1:1），得到了[{Au(C,N-C(6)H(4)CH(2)NMe(2)-2)}{Ag(X)(PPh(3))}{S(2)C=C{C(O)Me}(2)}] [X = OClO(3) (3), ONO(2) (4)]。通过将 2 与 PPh(3)反应（1:1），也可以得到 3。配合物Pd(C,N-C(6)H(4)CH(2)NR(2)-2)(μ-Cl)（R = Me, H）（i）与[Tl(2){S(2)C=C{C(O)Me}(2)}]和[PPN]Cl（0.5:1:1，PPN = Ph(3)P=N=PPh(3)）反应形成 PPN[Pd(C,N-C(6)H(4)CH(2)NR(2)-2){S,S-S(2)C=C{C(O)Me}(2)}] [R = H (5a), Me (5b)]，或（ii）与[Tl(2){S(2)C=C{C(O)Me}(2)}]（1:1）反应形成[{Pd(C,N-C(6)H(4)CH(2)NR(2)-2)}(2){μ-S,S,O-S(2)C=C{C(O)Me}(2)}] [R = H (6a), Me (6b)]。通过将相应的双核配合物 6a 或 6b 与[Pd(C,N-C(6)H(4)CH(2)NR(2)-2)(NCMe)(2)]ClO(4)（1:1）反应，可以制备出三核配合物[{Pd(C,N-C(6)H(4)CH(2)NR(2)-2)}(3){μ(3)-O,S,S,O-S(2)C=C{C(O)Me}(2)}]ClO(4) [R = H (7a), Me (7b)]。已经确定了 1、6b x CH(2)Cl(2)和 7b x CH(2)Cl(2)的晶体结构。进行了 NMR 研究以解释这些配合物在溶液中的行为。对于 R = Me（5b、6b、7b）的物种进行了 VT-NMR 和线形分析，允许估算这些交换过程的活化参数。
