Transition metals chalcogenolates

The aim of this chapter is to review the chemistry of chalcogenolates in the last 10 years. The more recent reviews in this field included chalcogenolates of the s-block elements,13,14 early transition metal thiolates,15 metal complexes with selenolate and tellurolate ligands,16 copper(I), lithium and magnesium thiolates,17 functionalized thiolate complexes,18 19 pentafluorobenzenethiolate platinum group compounds,20 tellurium derivatives,21 luminescent gold compounds,22 and complexes with lanthanide or actinide.23... 

Mixed alkali-metal chalcogenolates have been synthesized for main group elements, such as aluminium,54,55 germanium, and tin as (6) (Scheme 2),56 or transition metals such as zirconium,57 60 iron,61,62 vanadium,63 nickel,64 rhenium,65 and cobalt,66 or lanthanide metals.67,68... 

Towards Transition Metal Clusters by Reaction of Simple Metal Carbonyls with Chalcogenides and Chalcogenolates... 

Since the first reports of Pd(II)-catalyzed hydroselenation and hydrothiolation 1992, considerable investigations have accumulated experimental evidence for the mechanism, in particular for Type I mechanism. Each step of Type I mechanism, structures of active catalysts, the reaction of alkynes with the active catalysts, and the protonolysis of the resulting vinyl metal complexes, has been verified for Pd, Ni, Zr, Ln, and An-catalyzed hydrochalcogenations by isolation of intermediates, isotope-labeled experiments, and kinetic studies. With regard to Type II mechanism, while the initial oxidative addition of REH (E = S, Se) to a low-valent transition metal catalyst (metal = Pd and Pt) has been verified by direct (for Pt) or indirect (for Pd) experimental evidence, the following steps of alkyne insertion to chalcogenolate-hydrido complex and reductive elimination of resultant vinyl metal complexes leave room for further mechanistic investigations to obtain direct evidence. On the other hand, a hybrid mechanism of Type I and Type II has been clarified for the hydrothiolation with Rh(I) complexes. 

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