Chalcogenolates

Nakamura, T., Miyamae, T, Yoshimura, D., Kobayashi, N., Nozoye, H. and Matsumoto, M. (2005) Alkyl Chain Conformation and the Electronic Structure of Octyl Heavy Chalcogenolate Monolayers Adsorbed on Au(lll). Langmuir, 21, 5026-5033. 

Where more than one chalcogenolate is present, averaged values are given. 

Polymer formation is still observed with some sterically hindered thiolates, 2,4,6-Ao-propyl thiophenolate, and 2,4,6-trimethyl thiophenolate complexes have been studied. They can be synthesized by the reaction of Zn[N(SiMe3)2]2 with the appropriate arene chalcogenol. With the least steric bulk, the trimethyl derivative forms coordination polymers that can only be dissolved in strongly coordinating solvents. The iso-propyl derivative is more soluble forming oligomers in solution. 1... 

Far fewer structural studies have been conducted for the alkali metal chalcogenolates Se-M and Te-M. Nevertheless, the general aggregation patterns emerging are similar to those for S-M complexes, with solvated monomers and ring dimers being the dominant aggregation states for the reported structures.404... 

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... 

The starting material is always the chalcogenol and, consequently, is more used for thiols than selenols and tellurols. There are several types of reactions depending if the starting materials are metal hydrides (hydrogen elimination), complexes with M C (alkane elimination), M-N (transamination), or M-O (hydrolysis) bonds. 

The direct reaction of the metal with the chalcogenol is accessible for the heavy alkali metals, which are more reactive and also for the alkaline earth elements. 

This is a widely used preparation route towards metal chalcogenolates since the alkali compounds, mainly lithium and sodium derivatives, react with halogen complexes of almost any metal. The chalcogenols in the presence of a base can be used to scavenge the hydrogen halide. 

Several main group metal chalcogenolates can be used as starting materials to obtain other metal chalcogenolate derivatives. 

For sodium and potassium chalcogenolates, donor influence on structural pattern has been explored with a special emphasis in donor hapticity. Thus, crown ether complexation allows the isolation of monomeric species, such as [K(SCPh3)(18-crown-6)Lra] (L=thf, CgH6, hmpa, n = 0.5 L=toluene, n = l),36 [K(SMes )(dibenzo-18-crown-6)(thf)],45 [K(STrip)(dibenzo-18-crown-... 

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... 

Dinuclear complexes have been reported in which the chalcogenolates act as bridging ligands between the metal centres as in [Zn p-SSif O Bu)3 (acac)]2,136... 

The chemistry of the chalcogenolate compounds of these elements is dominated for the seek of molecular precursors for the deposition of 13/16 chalcogenide semiconductors by MOCVD or related techniques.159... 

These metals form chalcogenolate complexes in several oxidation states, and from the application-oriented point of view manganese compounds have been synthesized as models for hydrodesulfurization processes and rhenium and technetium derivatives as models for radiopharmaceuticals. 

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