Silver® thiolate ligands

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... 

The structure of (3-methylpentane-3-thiolato)silver(I) was found to consist of cores of chains, which were approximately linear. Each chain contained two separate strands, with alternating silver atoms and double bridged thiolate ligands, which were intertwined. Of interest was the unprecedented absence of any silver-sulfur bonding between chains.302... 

Other metallic clusters that have been demonstrated to show the QDL effect are palladium [116, 117], silver [118] and copper [119]. Palladium MFCs capped with mixed monolayers of hexanethiolate/dodecanethiolate and ferrocene thiolate ligands are prepared in a manner similar to that employed for gold MFCs. The DPV studies exhibit a quantized charging effect but the current peaks are not as well defined as those observed for Au-MPCs. Capacitance values of the order of 0.35 aF are obtained, indicating smaller core sizes or thicker monolayer dielectrics [116]. 

It has long been known that thiolate ligands (RS ), which are formally derived from thiols (RSH) by deprotonation, are well suited to form metal complexes (1). Specific reviews of this area have covered the structural chemistry of metal thiolates (la), the coordination chemistry of metal thiolates from a bioinorganic perspective (lb), transition metal thiolates (lc), and, most recently, early transition metal thiolates (Id). Because of potential thione-thiol tautomerism, a review dealing with complexes of heterocylic thione donors (le) is also relevant. This chapter concentrates on thiolate complexes of copper , lithium, and magnesium, but we also mention, for comparison or contrast, many related species of silver and gold and of some complexes that contain selenolate and tellurolate ligands. However, it should be emphasized that we have not attempted a comprehensive literature search outside the primary field of interest. 

Examples of the successful application of this method are the use of cop-per(II) acetate for the preparation of neutral complexes [Cu(SR)] (R = aryl, alkyl no base needed) (46), and the use of copper(II) nitrate for the synthesis of anionic species [Cu4(SPh))6]2 and [Cu5(SPh)7]2- (47, 48), as well as of the cationic species [Cu,(SC5H4NH)3]+ (49). The latter complex is interesting in that each thiolate ligand is neutral due to protonation of the pyridine nitrogen atom. Similarly, silver nitrate has been used to prepare several neutral alkyl-thiolato silver complexes (33). The use of copper(I) oxide was reported in the synthesis of a family of copper(I) arenethiolates containing intramolecularly... 

Figure 4 Comparison of copper and silver thiolate complexes of the same thiolate ligand and with the same formula unit. Perspective view of (a) [Cu(SC6H4-o-SiMe3)]i2 and (b) [ Ag(SC5H4-o-SiMe3) 4]2, highlighting the CU12S12 core and the fusing of two Ag4S4 units via Ag S secondary interactions (3.05...

Other Applications. TBST is widely used as a thiolate ligand for the s)mthesis of various metal thiolates as exemplified by the formation of Zn(II) thiolate 31 (eq 13) and silver(II) complex 32 (eq 14). ... 

The most thoroughly studied mixed S jA-ligand is pyridine-2-thiolate because of its versatile coordination modes. The compound [Ag(SPy)] has a graphite-like array of silver(I) ions and has a semiconductor behavior. The PyS ligand acts as a fi3-N,S,S bridge. [Ag5(SPy)(HSPy)BF4] has a layered structure with the coordination modes of PyS showed in Figure 14.1 04... 

As regards other coordination compounds of silver, electrochemical synthesis of metallic (e.g. Ag and Cu) complexes of bidentate thiolates containing nitrogen as an additional donor atom has been described by Garcia-Vasquez etal. [390]. Also Marquez and Anacona [391] have prepared and electrochemically studied sil-ver(I) complex of heptaaza quinquedentate macrocyclic ligand. It has been shown that the reversible one-electron oxidation wave at -1-0.75 V (versus Ag AgBF4) corresponds to the formation of a ligand-radical cation. Other applications of coordination silver compounds in electrochemistry include, for example, a reference electrode for aprotic media based on Ag(I) complex with cryptand 222, proposed by Lewandowski etal. [392]. Potential of this electrode was less sensitive to the impurities and the solvent than the conventional Ag/Ag+ electrode. 

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