Thiolate structures

Many different applications for gold cysteine nanoclusters have been proposed. One application is the use of citrate capped nanoparticles as sensors for the detection of thiol containing stractures. This application rehes on the fact that thiols can easily displace oxygen coordinated moieties. Zhong et al. have studied this process between cysteine and homocysteine to develop an assay for the homocysteine biomarker, a correlate to cardiovascular disease. When citrate stabilized particles of 13 run were incubated with either thiolate structure, the solution color changed from a dark red to a deep blue. The displacement of citrate by these moieties resulted... 

Reports that thermolysis of metal chalcogenolate complexes offers a low-temperature route to the synthesis of novel solid state materials (32) is also stimulating research in this area. As is the case with copper(I) thiolates, lithium thiolates are often aggregated species (Section III.C) and from the few magnesium thiolate structures known (Section III.D) one sees a preference for monomeric and dimeric formulations when bulky substituents are present. 

An analysis of the electronic structure in these complexes using Resonance Raman, EPR and Density Functional Theory (DFT) calculations provide evidence for tautomers depicted in Scheme 2.41 as an admixture of a thione-thiolate structure, which can be considered to result from electron density distributed into the quinoxaline structure from partial thiolate to thione oxidation (Scheme 2.41). ... 

Scheme 2.41 Asymmetry of the dithiolene chelates explained by an admixture of resonance forms, the thione-thiolate (structure B) and the dithiolate (structure A).

H. Antelmann and C. J. Hamilton, Bacterial Mechanisms of Reversible Protein S-Thiolation Structural and Mechanistic Insights into Mycoredox-ins. Mol Microbiol, 2012, 86, 759. 

Tetrazolium-5-thiolate, 2,3-diphenyl-structure, 5, 793 synthesis, 5, 827 Tetrazolium ylides synthesis, 5, 793, 827... 

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. 

They doubtless owe their stability to the bulk of the aryl thiolate ligand they have tbp structures with equatorial nitrile that can be displaced by CO to give rare carbonyls of a metal in the +4 oxidation state. 

Like gold, silver readily forms insoluble (yellow) thiolates [Ag(SR)] primary alkylthiolates are thought to have non-molecular structures but with bulky tertiary alkyls (n = 8), probably having a cyclic structure. Addition of excess thiolate leads to the formation of clusters like Ag6(SPh)g, Ag5(SPh)7 and Ag5(SBu )6 (phosphine adducts are known, too). 

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