Rhenium complexes sulfides

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Complex 376 can be prepared from enantiomerically pure rhenium precursor 381. The former can be deprotonated at low temperatures initiating the [2,3]-sigmatropic rearrangement to diastereomerically pure homoallylic sulfide complex 377. After S-alkylation, cyanide treatment releases the S ligand as product 379. As an extension of this work the authors showed that iron and ruthenium complexes can be used, too [219]. 

A connectivity of 1 is given for side chain metal-containing polymers as 1 in which the metal complex is connected via one bond to the main chain [11]. Additional examples for other connectivities are (Fig. 1-8) connectivity 2 in metal(yne)s 2 [12] connectivity 3 in arsenic(III) sulfide 3 connectivity 4 in a polymeric methyl rhenium oxide of the formula Ho.5[(CH3)o.92Re03] co 4 [13] or polymeric phthalocyanines 5 [14] connectivity 8 in lanthanide complexes of bis(tetradendate) Schiff base bridging ligands 6 [15]. 

In contrast to the synthetic accessibility of the above complexes using solution approaches, the synthesis of octahedral rhenium chalcogenide clusters requires the implementation of high temperature solid-state reactions, or the conversion of cluster-containing solids into soluble molecular species by the methods of cluster excision or dimensional reduction (see Section 7.2.2.1.8). While cluster excision has produced the mixed sulfide(selenide)-chloride clusters [Re6E4+ Clio 2 ] " ( = 1-3), the latter approach has led to the isolation of complexes with rhenium-chalcogenide cores [RegEgXg] - (E = S, Se X = C1, Br, I). 

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