Chalcogenolates synthesis

Hirpo, W. Dhingra, S. Sutorik, A. C. Kanatzidis, M. G. 1993. Synthesis of mixed copper-indium chalcogenolates. Single-source precursors for the photovoltaic materials CuInQ2 (Q = S, Se)./. Am. Chem. Soc. 115 1597-1599. 

Synthesis, photophysical, and electrochemical properties of dinuclear Cd(II) diimine complexes with bridging chalcogenolate ligands were described [91]. 

The synthesis generally involves reaction of either the ferrocenyl chalcogenols and l,l -ferrocenylene dichalcogenols, Fc-EH and fc(EH)2, or (preferably) the corresponding lithium derivatives, Fc-ELi and fc(ELi)2, with halides such as acid chlorides, non-metal chlorides and chloro metal complexes (E = S, Se, Te). 

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. 

Braga, A.L., Alves, E.E, Silveha, C.C., and de Andrade, L.H., Stereoselective addition of sodium organyl chalcogenolates to alkynylphosphonates. Synthesis of diethyl 2-(organyl)-2-(organochalcog-enyl)vinylphosphonates. Tetrahedron Lett., 41, 161, 2000. 

Substitution reactions involving silylated chalcogen reagents represent a powerful approach in metal-group-XVI cluster synthesis.Compounds such as E(TMS)2 and RE-TMS react readily with metal salts to form metal chalcogenide or chalcogenolate bonds (Equations (13)-(15)). The driving force for the reaction is the thermodynamically favorable formation of an X—Si bond and elimination of X-TMS (where X = halide, OAc, etc.). 

The use of silylated chalcogen reagents in the synthesis of chalcogen-bridged metal clusters has produced a remarkable number of complexes with a variety of structural types. The nuclearities and structures of these complexes can be highly dependent on the reaction conditions, the steric demands of the ancillary and/or chalcogenolate ligands, as well as the ratio M E. Complexes... 

The first report outlining the synthesis of a homoleptic product was the synthesis by Bochkarev of the divalent compound (Yb(EBu)2 E = S, Se), prepared by a proton-transfer reaction of an amido precursor with HEBu. This was followed by the metatiietical synthesis of Ln(SR)6 and compounds of the heavier chalcogenolates (Ln(EC6H3R3)2 (E = Se, Te R = Me). " The structure of the thiolate compound was described, but stmctural characterization of selenolate and tellurolate compounds did not appear until later, when the E-Si(SiMes)3 ligand was introduced to the Ln field, and new synthetic approaches to complexes of the EPh ligand were developed. 

Fluorinated chalcogenolates have been investigated as an alternative approach to the synthesis of soluble products. The Teflon-like character of tiie C6F5 moiety reduces intermolecular attractions and leads to the formation of hydrocarbon-soluble products. Thiolates have been investigated most extensively, and there are descriptions of both Ln(SC6F5)2 and Ln(SC6F5)3. These compounds have to be prepared with transmetallation reactions (Reaction 7), because attempts to reductively cleave disulfide bonds with elemental Ln leads to the formation of metal sources that appear to be passivated with a fluoride film. 

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