Metal thiolates structural chemistry

At present, our knowledge about the structure of the Cu -containing manunahan MT-1 and MT-2 isoforms is limited to the fact that fully Cu-loaded MT form contains 12 Cu ions organized in two metal-thiolate clusters, where, in contrast to divalent metal ions, the monovalent copper ions are coordinated by two or three cysteine ligands (see Copper Inorganic Coordination Chemistry)... 

The synthesis, structures, and reactivities of metal thiolates with group 4 and 5 metals, and the synthesis and study of copper-thiolates have been reviewed. Hg thiolate chemistry has been reviewed and related to the binding of Hg in vivo by metalloregulatory proteins. A range of two-, three-, and four-coordinate Hg thiolate complexes has been prepared, and comparisons with the metalloregulatory protein, Hg-MerR,... 

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. 

The next increase in aggregation state of Group 11 (IB) metal thiolates affords pentameric structures, but to the best of our knowledge a structurally characterized species of this type is unknown. In organocopper(I) chemistry, the only example is that of mesitylcopper [Cu5(C6H2Me3-2,4,6)5] (125), which has a structure based on an open Cu5C5 10-membered heterocycle. 

Present structural and spectroscopic data on the metal coordination in MTs indicate that metal binding is almost exclusively due to the cysteinyl thiolate sulfur atoms of the peptide chain the corresponding metal aggregates should therefore find a parallel in metal-thiolate chemistry. The only exception to this is the bacterial SmtA, in which it might be considered that two histidine residues play the role of two terminal cysteine ligands. In fact, interest in the extensive family of metal thiolates has mainly been fuelled in recent decades by structural or bioinorganic objec-... 

Dance, I.G. (1986) TTie structural chemistry of metal thiolate complexes . Polyhedron, 5, 1037-1104. 

Cadmium thiolates considered here include those compounds that, if mononuclear, only involve ligation by organothiolate anions (RS ) and, if polynuclear, only contain these groups as skeletal bridging ligands. A nice review on the structural chemistry of metal thiolate complexes was published in 1986 by Dance [80],... 

---