Coordination chemistry of 3-and 4-mercaptobenzoate ligands: Versatile hydrogen-bonding isomers of the thiosalicylate (2-mercaptobenzoate) ligand

This review summarises the coordination chemistry of the isomeric 3- and 4-mercaptobenzoate ligands, derived from HSC6H4COOH, being isomers of the widely-studied 2-mercaptobenzoate (thiosalicylate) ligand. The 3- and 4-mercaptobenzoate ligands show a wide range of coordination modes, including monodentate (through either S or less commonly O), chelation through the carboxylate group alone, as well as a wide range of bridging modes. However, S, O-chelation, which is prevalent for thiosalicylate complexes, is not found in the 3MBA and 4MBA isomers. In the solid-state, complexes of 3MBA and 4MBA ligands containing protonated carboxylic acid groups typically undergo aggregation through formation of classical hydrogen-bonded carboxylic acid dimer motifs, which can be supplemented by additional interactions such as aurophilic (Au center dot center dot center dot Au) interactions in the case of gold(I) complexes. The hybrid hard-soft nature of 3MBA and 4MBA ligands facilitates the use of these ligands in the construction of early-late heterobimetallic complexes. These ligands also find numerous applications (such as the protection of metallic gold and silver nanoparticles), which are especially prevalent for 4MBA where the para carboxylate/carboxylic acid group is remote from the sulfur coordination site. (C) 2017 Elsevier B.V. All rights reserved.