Abstract
AbstractReaction of the complex [(TPA)Zn(H2O)]2+ [TPA = tris(2‐pyridylmethyl)amine] with hydrogen sulfide in aqueous buffered solution gives the corresponding monomeric hydrogensulfido complex [(TPA)Zn(SH)]+, which was fully characterized, including by XRD. This complex is stable at neutral pH, but decomposes under basic conditions to yield the free ligand and zinc sulfide, and under acidic conditions to give hydrogen sulfide and the starting aqua complex. In organic solvents, the coordinated sulfur atom reacts with electrophiles such as methylmethanethiosulfonate to yield methyltrisulfide. Reaction with the hydroxo complex [(TpPh,Me)Zn(OH)] [TpPh,Me = hydridotris{(5‐methyl‐3‐phenyl)pyrazolyl}borate] promotes the formation of the unsymmetrical dinuclear μ‐sulfido species [(TPA)Zn–S–Zn(TpPh,Me)]+, which, upon treatment with one molar equivalent of trifluoroacetic acid, dissociates into [(TpPh,Me)Zn(SH)] and [(TPA)Zn(CF3CO2)]+, resulting in the transfer of the hydrogensulfido ligand from one zinc center to another.
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