Magnesium thiolates structures

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. 

The chemistry of alkaline-earth chacogenolates have been developed from the nineties with the structural characterization of the first magnesium thiolate in 1990,69 magnesium and calcium tellurolates in 1992,70,71 and the first magnesium and strontium selenolates in 1994.72... 

Within this overview of copper(I), lithium, and magnesium thiolate complexes, one of the aims is to highlight the influence that (intramolecular) nitrogen coordination exerts on the structure of such species, since intermolecular (auxiliary) coordination of heteroatoms often leads to poorly defined species. An example of this poor species definition is the reaction behavior of polymeric copper(I) thiophenolate, [Cu(SPh)]. with triphenylphosphine Several P-coordinated aggregates with variable stoichiometry were reported (Scheme 1) (27-29). This behavior makes it difficult to study one specific species in cop-per(I) thiolate catalyzed organic reactions since equilibria are likely to occur. 

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. 

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