Thiolate complexes

The excited state of the complex Pt(4,7-diphenyl-1,10-phenanthroline)( 1,2-dicyano-l,2-ethylenethiolate) (Pt(dpphen)(mnt)) is oxidatively quenched by o-nitrobenzaldehyde [Eq. (3.46)], and reductively quenched by dimethylaniline [Eq. (3.47)], showing that excited state photoredox chemistry can be carried out with this series of platinum complexes  

The photochemistry of dithiolene complexes of selected second- and third-row transition metal ions have also been investigated. Like the complexes with nickel, dithiolene complexes of palladium, platinum, molybdenum, and tungsten catalyze the formation of hydrogen from water when aqueous solutions of the complexes are irradiated at wavelengths shorter than 290 Tetrahydrofiiran is 

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Quite a number of asymmetric thiol conjugate addition reactions are known [84], but previous examples of enantioselective thiol conjugate additions were based on the activation of thiol nucleophiles by use of chiral base catalysts such as amino alcohols [85], the lithium thiolate complex of amino bisether [86], and a lanthanide tris(binaphthoxide) [87]. No examples have been reported for the enantioselective thiol conjugate additions through the activation of acceptors by the aid of chiral Lewis acid catalysts. We therefore focussed on the potential of J ,J -DBFOX/ Ph aqua complex catalysts as highly tolerant chiral Lewis acid catalyst in thiol conjugate addition reactions. 

Both cis- and (rans-structures are possible RuH2(PMe3)4 is cis (Ru-H 1.507, 1.659 A, Ru-P 2.276-2.306 A) [90] while spectra show that RuH2(PF3)4 and others have this configuration. RuH2[PPh(OEt)2]4 is definitely trans (X-ray) with Ru-H 1.6 A, Ru-P 2.272 A. Many diphosphines form dihydrides. Ru(dmpe)2H2 has been a useful starting material for the synthesis of thiolate complexes [91] such as fra s-Ru(SPh)2(dmpe)2. 

We found recently that the viscosity (//vac) of the colloidal thiolate precursor is a key parameter in controlling the shape of the nanoproducts in the solventless method [8]. Uniform nanowires, rods, or spheres could be made from the corresponding precursors that came from the solutions with different viscosities. The viscosity is a measure of the polymerization of the metal-thiolate complexes. Accordingly, the precursor with the highest viscosity produces nanowires (Fig. 20.5 a), and with decreases in the viscosity, the product morphology changes to rods (Fig. 20.5b) and then spheres (Fig. 20.5c). 

In recent years, several model complexes have been synthesized and studied to understand the properties of these complexes, for example, the influence of S- or N-ligands or NO-releasing abilities [119]. It is not always easy to determine the electronic character of the NO-ligands in nitrosyliron complexes thus, forms of NO [120], neutral NO, or NO [121] have been postulated depending on each complex. Similarly, it is difficult to determine the oxidation state of Fe therefore, these complexes are categorized in the Enemark-Feltham notation [122], where the number of rf-electrons of Fe is indicated. In studies on the nitrosylation pathway of thiolate complexes, Liaw et al. could show that the nitrosylation of complexes [Fe(SR)4] (R = Ph, Et) led to the formation of air- and light-sensitive mono-nitrosyl complexes [Fe(NO)(SR)3] in which tetrathiolate iron(+3) complexes were reduced to Fe(+2) under formation of (SR)2. Further nitrosylation by NO yields the dinitrosyl complexes [(SR)2Fe(NO)2], while nitrosylation by NO forms the neutral complex [Fe(NO)2(SR)2] and subsequently Roussin s red ester [Fe2(p-SR)2(NO)4] under reductive elimination forming (SR)2. Thus, nitrosylation of biomimetic oxidized- and reduced-form rubredoxin was mimicked [121]. Lip-pard et al. showed that dinuclear Fe-clusters are susceptible to disassembly in the presence of NO [123]. 

Robbins, A.H. and Stout, C.D. (1992) Metallothioneins Synthesis, Structure and Properhes of Metallothioneins, Phytochelatins, and Metal-Thiolate Complexes (eds M.l. ShDman, C.F. Shawlll and KT. Suzuki), VCH Publishers, Weinheim, pp. 31—54. 

Scheme 1. The solvent-free controlled thermolysis of gold(I) thiolate complex producing gold nanoparticles stabilized by alkyl groups derived from the precursor.

Scheme 2. Production of size-regulated gold nanoparticles stabilized by primary amines, tertiary amines, sulfides, and thiols formed by the controlled thermolysis of gold(I) thiolate complex in the presence of amine (reprinted from Ref. [11], 2005, with permission from Elsevier).

The square-planar Ir1 thiolate complex (391) has been prepared by the reaction of Pr(NO)Cl2(PPh3)2] with NaSmes (mes = C6H2Me3-2,4,6).635 reaction of (391) with propylene sulfide affords the Ir111 complex (392), as shown in Reaction Scheme 42. The X-ray structure of (392) confirms the square-pyramidal geometry of the Ir center and the bent nature of the Ir—N=0 linkage. 

Some mixed valence polynuclear thiolate complexes such as [Ni4(SC3H7)8Br] and [Ni4(SC3H7)8I] have been prepared and characterized by single-crystal X-ray methods.203... 

By oxidative addition of aryl sulphides to low-valent nickel complexes, a C—S bond cleavage occurs to form Ni11 thiolate complexes. For example, exposure of diaryl sulphides to [(But3P)3Ni0] leads to oxidative addition, with nickel inserting into the C—S bond (280).814... 

Silver(I) trifluoromethanethiolate (AgSCF3) has been used to prepare trifluoromethyl aryl sulfides by reaction with iodide.996 A mixed silver-zinc thiolate complex [Ag4Zn2(SC6H2-Pr -2,4,6)6(OTf)2] has been prepared by reaction of AgOTf with Zn[N(TMS)2]2 in the presence of the thiol.99 Solid-state 109Ag NMR can be a sensitive environment probe for silver thiolates,998 overall for biological thiolates ligands as cysteine,999 or proteins such as metallothionein.1000,1001... 

Gold(I) thiolate complexes have different stoichiometries, the neutral [Au(SR)(PR3)] complexes are very numerous and have been synthesized for a great variety of thiolate and tertiary phosphine ligands. The phosphine is usually PPh3 (otherwise state) and the substituent R in the thiolate moiety can be Me (PMe3),2779 Ph (PR 3 PPh3, TPA),2780-2784 2,4,6-C6H2R23 (R2 = Me,... 

Reviews on mercury—thiolate complexes and their bio-relevance333 and complexes with steric-ally hindered thiolate ligands have been published.334... 

Technetium complexes with thioethers in the strict sense, i.e., those without other donor groups in the ligand molecule, comprise homoleptic thioether nitridotechnetium(V) complexes [111], cationic mixed thioether/thiolate complexes of Tc(III) [112], and a cationic Tc(I) complex [113]. However, these latter compounds do not properly fall within the scope of Tc(V) compounds and are excluded from review. 

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