Thioether macrocyclic complexes structure

Thioether ligand complexes are not very common, however, studies since the mid 1990s have dramatically increased the number of structurally characterized examples. Almost all of these compounds are with chelate or macrocyclic ligands that will stabilize thioether coordination. Mixed donor multidentate ligands containing thioether donors will be discussed in Section 6.8.11. 

Shaw, J. L., Wolowska, J., Collison, D., etal., Redox non-innocence of thioether macrocycles Elucidation of the electronic structures of mononuclear complexes of gold (II) and silver(II). J Am. Chem. Soc. 2006, 128, 13827-13839. 

The charge-transfer complex of 1,4,7-trithiacyclononane 10 and I2 has been prepared by slow evaporation of solutions containing I2 and thioether macrocycle in CH2CI2. The structure of the complex showed two independent macrocycles in the asymmetric unit which are linked by a diiodine bridge. Asymmetric units are linked by iodine-iodine and sulfur-iodine interactions to form an extended array of linked macrocycles. The formation enthalpy ( AH = 35.0 kj mob1) and formation constant (K= 169 dm3 mol-1) of 1 1 adduct have been determined by electronic spectroscopy and compared to other polythia macrocycles of different sizes <1997JCD1337>. 

To gain insight into electron-transfer kinetics of copper(II/I) complexes of macrocyclic thioethers,446,447 Rorabacher and co-workers reported448,4 7 structures of five complexes (complexes (548)-(552)). 

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