Tellurol metal complexes

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... 

Arnold, John, The Chemistry of Metal Complexes with Selenolate and Tellurolate... 

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 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 lithium telluride substitutes TiCl3(THF)3 and (PhCH2)4M react with the tellurol, the [(Me3Si)3SiTe]4M derivatives complexing with isocyanides or dmpe, the latter inducing decomposition to the disilyl telluride and metal telluride97 (equation 48). 

Tellurolates replace chloride in transition metal halo complexes, in copper(I) chloride and in mercury(II) chloride. 

The oxidative addition of chalcogen-chalcogen bonds in RE—ER is widely applied in transition metal chemistry and is often a useful route for the preparation of thiolates, selenolates and, to a more limited extent, tellurolates. The oxidative addition of X2 = HO—OH and PhC(0)0—0C(0)Ph is also known and, in the case of Ptu complexes, gives predominantly trans products 47... 

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