0000000000496711
AUTHOR
Gérard Tainturier
Composés métallocèniques chalcogènés. Action des dihydrures de zirconocène et de hafnocène sur le soufre, le sélénium et le tellure
Resume Dimeric zirconocene and hafnocene dihydrides [(η 5 -RC 5 H 4 ) 2 M(H)(μ-H)] 2 (M = Zr, Hf) react with grey selenium or tellurium to afford the known four-membered bimetallacyclic compounds [(η 5 -RC 5 H 4 ) 2 M(μ-E)] 2 (E = Se, Te) as the sole organometallic products. In the case of sulfur the first step of the reaction is shown to involve the insertion of a chalcogen atom into the metal-hydrogen bonds to give the bis-hydrogenosulfide (η 5 -t-BuC 5 H 4 ) 2 M(SH) 2 (M = Zr, Hf), which reacts either with the starting dihydride to give [(η 5 -t-BuC 5 H 4 ) 2 M(μ-S)] 2 or with the unchanged sulfur to afford the metallacyclohexasulfane (η 5 -t-BuC 5 H 4 ) 2 MS 5 and hydrogen sulfide. Thes…
Regio- and stereo-selectivity in the induction of peroxisome proliferation by substituted hexanoic acids
Summary Quantitative structure-activity relationship is an effective tool in order to predict drug potency. A similar approach is actually developed for peroxisome proliferation induced by substituted carboxylic acids issued from plasticizer metabolism in rats. The study is focused on acids found in rat urine after adipic diester dosings. Size, location of the substituted group and length of the chain have been studied. 3-D structure has also been taken in account for 2-ethyl hexanoic acids. The results obtained so far demonstrate that peroxisome proliferation potencies of the considered acids are modified according structure changes. At this time location of the group along the chain appea…
Electrochemical modifications of proteins: disulfide bonds reduction
International audience; Electrochemical reduction of lysozyme disulfide bonds was achieved at pH between 10 and 11.Below pH 10, no disulfide bond cleavage was observed. At pH higher than 12, the cleavage of disulfide bonds is essentially due to hydrolysis. The addition of denaturant considerably enhanced the performance of the electrochemical device.
The preparation of four- and six-membered chalcogenametallacyclic derivatives of group 4 metallocenes
Abstract Four-membered metallacycles [(RC 5 H 4 ) 2 M(μ-E)] 2 (M = Zr, Hf; 1 , E = Se; 2 , E = S) were obtained by UV irradiation of dialkyl- or diaryl-metallocenes and equimolecular amounts of elemental chalcogen, but this method works only for bulky R groups. A more general route to compounds 1 and 2 involves the reaction of metallocene dichloride with chalcogenide anions. Six-membered metallacyclohexasulfanes (t-BuC 5 H 4 ) 2 MS 5 ( 3 , M = Zr, Hf) are obtained rather than compounds 2 when an excess of sulfur is used in the photolytic experiments, whereas compounds 1 were still formed when an excess of selenium was used. The observed difference is explained in terms of the solubility of …
Thermal stability and reaction of chalcogen-containing metallocenic compounds with elemental chalcogens
Abstract Dissymmetrical four-membered bimetallocenacycles (t-BuC 5 H 4 ) 2 M(μ-S) 2 M′-(RC 5 H 4 ) 2 (M, M′ = Zr, Hf; R = H, t-Bu) have been prepared and found to give redistribution products in solution at 190°C; identification of these products shows that the reaction involves exclusive cleavage of a metal-sulfur bond. Elemental sulfur and selenium react with chalcogen-containing complexes. The reaction is shown to involve the introduction of chalcogenic species in place of the σ-ligands of the complex to give either four-membered bimetallic complexes or catenated pentachalcogen metallocenic compounds. Some examples of insertion of sulfur and tellurium into the zirconium-methyl bond are a…