Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea, Universidad de Zaragoza-CSIC, E-50009 Zaragoza, Spain.
Inorg Chem. 2011 Oct 3;50(19):9533-44. doi: 10.1021/ic201245q. Epub 2011 Aug 23.
The reaction of [AuCl(P-N)], in which P-N represents a heterofunctional phosphine ligand, with pentafluorothiophenol, HSC(6)F(5), gives the thiolate gold derivatives [Au(SC(6)F(5))(P-N)] (P-N = PPh(2)py (1), PPh(2)CH(2)CH(2)py (2), or PPhpy(2) (3)). Complex [Au(SC(6)F(5))(PPh(2)py)] (1) reacts with [Au(OTf)(PPh(2)py)] in a 1:1 or 1:2 molar ratio to afford the di- or trinuclear species [Au(2)(μ-SC(6)F(5))(PPh(2)py)(2)]OTf (4) and Au(3)(μ(3)-SC(6)F(5))(PPh(2)py)(3)(2) (5), with the thiolate acting as a doubly or triply bridging ligand. The reactivity of the mononuclear compounds [Au(SC(6)F(5))(P-N)] toward silver or copper salts in different ratios has been investigated. Thus, the treatment of [Au(SC(6)F(5))(P-N)] with Ag(OTf) or [Cu(NCMe)(4)]PF(6) in a 1:1 molar ratio gives complexes of stoichiometry [AuAg(OTf)(μ-SC(6)F(5))(P-N)] (P-N = PPh(2)py (6), PPh(2)CH(2)CH(2)py (7), or PPhpy(2) (8)) or [AuCu(μ-SC(6)F(5))(P-N)(NCMe)]PF(6) (P-N = PPh(2)py (9), PPh(2)CH(2)CH(2)py (10), or PPhpy(2) (11)). These complexes crystallize as dimers and display different coordination modes of the silver or copper center, depending on the present functionalized phosphine ligand. The treatment of [Au(SC(6)F(5))(PPh(2)py)] with silver and copper compounds in other molar ratios has been carried out. In a 2:1 ratio, the complexes [Au(2)M(μ-SC(6)F(5))(2)(μ-PPh(2)py)(2)]X (M = Ag, X = OTf (12); M = Cu, X = PF(6) (13)) are obtained. The same reaction in a 4:3 molar ratio affords the species [Au(4)M(2)(μ-SC(6)F(5))(3)(μ-PPh(2)py)(4)]X(3) (M = Ag, X = OTf (14); M = Cu, X = PF(6) (15)). The crystal structures of some of these complexes reveal different interactions among the metallic d(10) centers. The complexes display dual emission. The band at higher energy has been attributed to intraligand (IL) transitions, and the one at lower energy has been assigned to a ligand to metal (LM) charge transfer process. The latter emission is modulated by the heterometal (silver or copper).
[AuCl(P-N)] 与五氟硫酚（HSC(6)F(5)）反应，生成硫醇基金衍生物 [Au(SC(6)F(5))(P-N)]（P-N = PPh(2)py (1)、PPh(2)CH(2)CH(2)py (2)或 PPhpy(2) (3)）。配合物[Au(SC(6)F(5))(PPh(2)py)]（1）与[Au(OTf)(PPh(2)py)]以 1:1 或 1:2 的摩尔比反应，生成二核或三核物种[Au(2)(μ-SC(6)F(5))(PPh(2)py)(2)]OTf（4）和Au(3)(μ(3)-SC(6)F(5))(PPh(2)py)(3)(2)（5），其中硫醇基充当双或三桥连配体。研究了单核化合物[Au(SC(6)F(5))(P-N)]与不同比例的银或铜盐的反应性。因此，[Au(SC(6)F(5))(P-N)]与 Ag(OTf)或[Cu(NCMe)(4)]PF(6)以 1:1 摩尔比处理，得到化学计量比为[AuAg(OTf)(μ-SC(6)F(5))(P-N)]（P-N = PPh(2)py (6)、PPh(2)CH(2)CH(2)py (7)或 PPhpy(2) (8)）或[AuCu(μ-SC(6)F(5))(P-N)(NCMe)]PF(6)（P-N = PPh(2)py (9)、PPh(2)CH(2)CH(2)py (10)或 PPhpy(2) (11)）的配合物。这些配合物结晶为二聚体，并显示出不同的银或铜中心配位模式，具体取决于存在的功能化膦配体。还进行了[Au(SC(6)F(5))(PPh(2)py)]与银和铜化合物以其他摩尔比的处理。在 2:1 的比例下，得到配合物[Au(2)M(μ-SC(6)F(5))(2)(μ-PPh(2)py)(2)]X（M = Ag，X = OTf（12）；M = Cu，X = PF(6)（13））。相同反应在 4:3 的摩尔比下得到物种[Au(4)M(2)(μ-SC(6)F(5))(3)(μ-PPh(2)py)(4)]X(3)（M = Ag，X = OTf（14）；M = Cu，X = PF(6)（15））。一些配合物的晶体结构揭示了金属 d(10)中心之间的不同相互作用。这些配合物具有双重发射。高能波段归因于内配体（IL）跃迁，而低能波段归因于配体到金属（LM）电荷转移过程。后者的发射被杂金属（银或铜）调制。
