Tellurium complexes metal clusters

It is evident from the above table that a considerable spread of chemical shift values is observed in tellurium-transition metal complexes, but the factors that determine the chemical shift are still poorly understood and data are not available for all known structural types. The most extensive compilations of data have been provided by Rauchfuss (187) and Herrmann (191), with the point being made in the former reference that chemical shifts are extremely sensitive to changes in cluster geometry. In principle, 12sTe NMR spectroscopy is a valuable method for studying tellurium-transition metal clusters in solution, but it is clear that more data are required before unambiguous structural assignments can be inferred. 

Within this context, the present article concentrates on transition metal cluster complexes of cobalt, iron and manganese with mixed chalcogen/carbonyl ligand spheres obtained by reaction of simple binary metal carbonyls with alkali-metal sulfides, alkali-metal thiolates or transition-metal thiolate complexes and their selenium or tellurium counterparts. 

In common with transition and other metals (Chapter 8), tellurium will form cluster complexes such as... 

Ten /13-TePh ligands adopt an unsymmetrical pattern of one shorter , one longer and one intermediate Cu-Te bonding distances. These distances (2.552(3)-2.708(3) A) are, expectedly, shorter than their Ag-Te counterparts, and reflect the difference between the ionic radii of the two metals.This contraction of the metal-tellurium bonding distances is reflected in the overall size of the cluster frame. Thus, for comparison, the Te4 - Te7 distance is 12.29 A in 5 and 12.95 A in 3a similarly the telluride ligands Tel5-- Tel6 are 7.72 A apart in the copper complex whereas they are separated by 8.81 A in the silver cluster 3a. 

The ability to control product formation, the reproducibility of results, and the relatively mild conditions under which the reactions proceed, have made cluster syntheses by this method very attractive. Furthermore, the starting materials are themselves readily prepared and easily stored and handled. This is especially valuable in metal telluride chemistry, in which suitable reagents for cluster syntheses are often unstable and must be generated in situ, leading to complex mixtures of reaction products. The use of the silylated tellurium reagents Te(TMS)2 and RTe-TMS has allowed access to a wealth of metal tellurium clusters with unique structures and properties. " ... 

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