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In search of complexes having [ZnN 3 S 2 ] cores in the monomeric form with trans-thiolate donor atoms, new sterically demanding tri- and pentadentate ligands containing biomimetic N 3 S 2  cores have been synthesized. The reaction of bis(2-mercapto-3,5-di-tert-butylaniline)zinc(II) with 2,6- diacetylpyridine leads to the formation of the zinc imine [Zn(py t BuN 2 Me 2 S 2 )] (3) which is stable and can be isolated and characterized in the solid state. Complex 3 can be converted to the zinc amine function [Zn(py t BuN 2 H 2 Me 2 S 2 )] (5) without losing the metal center using NaBH 4  in methanol solution. On the other hand, complex 3 can be demetallated in an acidic medium to give the tridentate bis-benzothiazoline ligand 4. Alternatively, ligand 4 can be obtained via condensation of 3,5-di-tertbutylmercaptoaniline with 2,6-diacetylpyridine in a 2:1 molar ratio. Opening the bis-benzothiazoline ligand 4 either by reduction with NaBH4 in methanol or by zinc acetate leads to the formation of the pentadentate dithiole-amine ligand py t BuN 2 H 2 Me 2 S 2- H 2  (6), and the zinc imine complex 3, respectively. Ligand 6 can also be obtained via demetallation of the zinc amine complex 5 in acidic medium. All compounds have been characterized using spectroscopic methods and elemental analysis, and also by using DFT (B3LYP/6-31G ∗)  calculations in combination with experimental NMR data.

Five-coordinate Zinc(II) Complexes Containing Sterically Demanding Bio-mimetic N 3 S 2 Ligands. Syntheses, Characterization and DFT Calculations