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A new N2S ligand bis(pyridyl)(2-mercapto-1-methylimidazolyl)methane (2, Py2MeImS) has been synthesized and characterized. Treatment of this ligand with bromide and triflate salts of Zn(II) results in the complexes (Py2MeImS)ZnBr2 (3) and [(Py2MeImS)2Zn](OTf)2 (4), respectively. The solid-state structure of (Py2MeImS)ZnBr2 shows bidentate N,N-coordination of Py2MeImS to the zinc ion, with the sulfur atom of the 2-mercaptoimidazole moiety uncoordinated. Two conformers of 3 rapidly interconvert in solution at room temperature, and variable temperature NMR studies and DFT calculations were used to help assign the likely identity of these conformers. In contrast, the crystal structure of [(Py2MeImS)2Zn] (OTf)2 exhibits a zinc ion with a distorted octahedral geometry where the two sulfur atoms of the two ligands are coordinated to the zinc center in a cis-configuration. Even though the cis-isomer (4-cis) is calculated to be lower in energy than the trans-isomer (4-trans), the low temperature 1H NMR spectrum of 4 reveals a single symmetric species that is inconsistent with the cis-isomer observed in the solid-state structure. DFT calculations propose alternative higher energy structures, including a trans-configuration of the coordinated S-atoms of the two Py2MeImS ligands, as well as structures in which the 2-mercaptoimidazole groups are no longer coordinated to the zinc(II) center. These studies provide valuable insight into the potential binding modes of this new ligand and its behavior in solution.

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