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Synthesis, Stability, and Reactivity of [(TPA)Zn(SH)] + in Aqueous and Organic Solutions
Author(s) -
Galardon Erwan,
Tomas Alain,
Roussel Pascal,
Artaud Isabelle
Publication year - 2011
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201100527
Subject(s) - chemistry , aqueous solution , ligand (biochemistry) , zinc , inorganic chemistry , medicinal chemistry , electrophile , sulfide , reactivity (psychology) , hydrogen sulfide , amine gas treating , sulfur , yield (engineering) , monomer , carbonyl sulfide , trifluoroacetic acid , polymer chemistry , organic chemistry , catalysis , medicine , biochemistry , receptor , alternative medicine , materials science , polymer , pathology , metallurgy
Reaction of the complex [(TPA)Zn(H 2 O)] 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 [(Tp Ph,Me )Zn(OH)] [Tp Ph,Me = hydridotris{(5‐methyl‐3‐phenyl)pyrazolyl}borate] promotes the formation of the unsymmetrical dinuclear μ‐sulfido species [(TPA)Zn–S–Zn(Tp Ph,Me )] + , which, upon treatment with one molar equivalent of trifluoroacetic acid, dissociates into [(Tp Ph,Me )Zn(SH)] and [(TPA)Zn(CF 3 CO 2 )] + , resulting in the transfer of the hydrogensulfido ligand from one zinc center to another.