Thiolate crystal structures

Tzeng, B.-C., Yeh, H.-T., Huang, Y.-C., Chao, H.-Y., Lee, G.-H. and Peng, S.-M. (2003) A Luminescent Supermolecule with Gold(l) Quinoline-8-thiolate Crystal Structure, Spectroscopic and Photophysical Properties. Inorganic Chemistry, 42, 6008-6014. 

Nickel is found in thiolate/sulflde environment in the [NiFe]-hydrogenases and in CODH/ACS.33 In addition, either a mononuclear Ni-thiolate site or a dinuclear cysteine-S bridged structure are assumed plausible for the new class of Ni-containing superoxide dismutases, NiSOD (A).34 [NiFe]-hydrogenase catalyzes the two-electron redox chemistry of dihydrogen. Several crystal structures of [NiFe]-hydrogenases have demonstrated that the active site of the enzyme consists of a heterodinuclear Ni—Fe unit bound to thiolate sulfurs of cysteine residues with a Ni—Fe distance below 3 A (4) 35-39 This heterodinuclear active site has been the target of extensive model studies, which are summarized in Section 6.3.4.12.5. 

A template synthesis employing Ni(OAc)2, 2,5-dihydroxy-2,5-dimethyl-1,4-dithiane, and 3,3 -iminobis(propylamine) gave the water-soluble five-coordinate complex [Ni(495)], the crystal structure of which shows trigonal bipyramidal coordination of Ni11 with the central amine and terminal thiolates in plane and the two imino nitrogens in axial positions. Solvatochromism of the complex is interpreted in terms of S" H bonding, which may be of relevance to the catalytic cycle in hydrogenases.1341... 

Homoleptic silver(I) thiolates AgSR have been known and used for a long time,957,958 but until recently with little definitive information about their structures. They are insoluble or slightly soluble, yielding unreliable high molecular weights in solution, indicative of nonmolecular crystal structures. These compounds dissolve due to the presence of thiolate ions. 

Fig. 17. Schematic drawing of a predicted hexameric ring structure for a 1 1 gold(I)-thiolate (417) and found in the crystal structure of Au(I)-2,4,6-tri(isopropyl)thi-ophenolate (418).

Fig. 2 Crystal structure of a Au25(SR)i8 cluster (R is phenylethyl group) (a) the icosahedral Au13 core (b) the Aui3 core covered by 12 Au atoms (c) the whole Au25 cluster is protected by 18 thiolate ligands (for clarity, only S was shown, magenta, Au yellow, S)[19]...

The X-ray crystal structure shows that the two thiolate ligands bridge the... 

As mentioned earlier, the bulky terphenyl thiolate ligand -SC6H3-2,6-Mes2 has been shown to stabilize nominal two-coordination in transition metal complexes.53,54 Figure 30 represents the X-ray crystal structure of the iron derivative, Fe(SC6H3-2,6-Mes2)2.53... 

Only a few group 1 and 2 metal derivatives of selenolates have been structurally characterized. They are prepared with the same methods used for the thiolates.155,158 At present there are no crystal structures of lithium terphenyl selenolates. However, the potassium and rubidium salts, which are dimeric, have been structurally characterized.155 They are isomorphous, both to each other and to the closely related thiolate analogues.1533 Currently, there are no reported terphenylselenolates reported for the alkaline-earth metals. 

The crystal structures of sodium l,2,3,4-thiatriazole-5-thiolate (5) dihydrate and 5-benzoylthio-1,2,3,4-thiatriazole have been investigated and atomic parameters, bond lengths and bond angles are reported (Figure 4) <91AX(C)1018>. The compounds have the expected cyclic structures. 

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