Rhenium halo complexes

The rates of ligand exchange of 0.01 M hexahalo-technetium(IV) and hexa-halo-rhenium(IV) complexes were measured in the 8 M solutions of their corresponding acid at 60 °C. The overall exchange rates R were determined as follows ... 

Herrmann and co-workers showed that the 17-electron complex 62 may be subjected to electrochemical oxidation as well as reduction (54.55). The redox potentials of the respective halo complexes follow the expected trend for change in the halide ligands. In accordance with these electrochemical studies, both chemical oxidation and reduction reactions of 62 were found [Eqs. (49) and (50)]. Oxidation of the rhenium complex Re(CCMe3)(// -C5Me5)Cl2 by dioxygen results in cleavage of the neopentylidyne ligand from the metal center as pivalic anhydride and pivaloyl chloride. 

A number of complexes can be derived from the trinuclear and dinuclear rhenium(m) halides and halo complexes (page 979) with retention of the Re3 and Re2 units. 

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