Synthesis, characterization, and reactivity of alkyldisulfanido zinc complexes.
The alkyldisulfanido zinc complexes Tp(iPr,iPr)Zn(SSR) and Tp(Ph,Me)Zn(SSR) where Tp(iPr,iPr) is hydridotris-((3,5-isopropyl)pyrazolyl)borate, Tp(Ph,Me) is hydridotris-((3-phenyl,5-methyl)pyrazolyl)borate, and (SSR) is tert-butyldisulfanido or triphenylmethanedisulfanido were synthesized by reaction between the corresponding hydroxo complexes TpZn(OH) and the synthetic persulfide RSSH. All the complexes were characterized by elemental analysis and (1)H NMR spectroscopy, and representative members of the class were also structurally characterized. The reactivity of the alkyldisulfanido TpZn(SSR) complexes with thiols was studied. In the absence of base, a simple exchange reaction between the alkyldisulfanido ligand and the thiol was observed in dichloromethane; when in the presence of base, the corresponding hydrogen(sulfido) complexes TpZn(SH) were obtained. The mechanism of the latter reaction has been studied and does not involve the coordinated alkyldisulfanido group. Reaction of the hydrogen(sulfido) complexes Tp(iPr,iPr)Zn(SH) with the thiosulfonate PhCH(2)S-SO(2)CF(3) did not yield the expected alkyldisulfanido complex but benzyltrisulfide and a new complex tentatively assigned as Tp(iPr,iPr)Zn(O(2)SCF(3)).
Galardon
Erwan
E
Laboratoire de Chimie et Biochimie Pharmacologique et Toxicologique, UMR 8601 CNRS, Université Paris Descartes, 45 rue des Saints Pères, 75270 Paris cedex 06, France.
Tomas
Alain
A
Selkti
Mohamed
M
Roussel
Pascal
P
Artaud
Isabelle
I
D018360:Crystallography, X-Ray; D006860:Hydrogen Bonding; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D017550:Spectroscopy, Fourier Transform Infrared; D013440:Sulfides / Q000737:chemistry*; D017967:Zinc Compounds / Q000138:chemical synthesis / Q000737:chemistry*
D013440:Sulfides; D017967:Zinc Compounds