L. Gorrichon-Guigon

Etude par RMN 13C Et 199Hg de composes oxobromo- et dioxomercuriques

Abstract Organomercuric compounds of the general formula and [RCOCH(R′)] 2 Hg, obtained from three ketones, 2,2-dimethyl 3-pentanone, 1-mesityl 1-propanone and 1-mesityl 1-ethanone, have been studied by 13 C and 199 Hg NMR techniques. Coupling constants J (CHg) and J (HgH) are consistent with C-metalated species; in each case the values of δ(C(2)) and J (C(2)H) observed are higher than expected for purely sp 3 carbon. The contribution of O-metalated species and hyperconjugative effects are discussed. For two dioxomercuric compounds (R′  Me, R  t-Bu, mesityl) the existence of diastereoisomers is suggested from 199 Hg NMR data.

Une nouvelle classe d′inhibiteurs irréversibles les sulfinamoylesters précurseurs de sulfines

Abstract Tert -butyl N-aryl sulfinamoyl acetates are hydrolysed in aqueous basic media following a bimolecular elimination process, via an intermediate sulfine species. The use of sulfinamoyl compounds as irreversible inactivators for zinc-metallo-enzymes is emphasized.

Zinc(II) complexes of sulfinamides—I. N-Phenyl 2-propane sulfinamide, t-butyl N-phenyl and t-butyl N-cyclohexyl sulfinamoyl acetates

Abstract The zinc(II) complexes of the title sulfinamoyl compounds L 2 ·ZnX 2 (X = Cl, Br) were prepared and studied by NMR and i.r. methods. All the complexes have a tetrahedral [O 2 X 2 ] coordination and NH . . X hydrogen bonding.

Zinc(II) complexes of sulfinamides—II. t-Butyl N-(hydroxyphenyl) and t-butyl N-(o-aminophenyl) sulfinamoyl acetates

Abstract The ZnBr 2 complexes of the four title sulfinamoylesters were formed and investigated by NMR and i.r. techniques. The stoichiometry of the complexes greatly depends on the position of the amino or hydroxyl substituents on the aromatic ring. Nevertheless, the occurrence of a tetracoordinated zinc atom is suggested for all the complexes.

Etude spectroscopique de la structure des derives oxobromo- et dioxo-mercuriques de la dimethyl-2,2-pentanone-3 a l'etat solide et dissous

Abstract Association capabilities of oxobromomercuric and dioxomercuric compounds I and II have been investigated by cryoscopic methods, 1 H NMR, IR and Raman spectroscopy. The association degree n is concentration dependent for I in C 6 H 6 while no variation of n is observed in the case of II for which the value of n is close to one. Similarly 1 H NMR data show diminuation of 2 J (HgH) and 3 J (HgH) upon solution of I in C 6 D 6 or CDCl 3 while no modification of 2 J and 3 J is noticed for II. Using C 6 D 6 as solvent, important shielding of δ(CH) and δ(CH 3 ) is found in the spectra; these effects are smaller for δ(CH 3 ) than for δ(CH) and less clear for II than for I. IR and Raman spectra of I and II in the solid state show associative intermolecular interactions Hg…Br (in I), Hg…O intramolecular interactions and a linear structure of CHgC in II. The splitting of v (CO) frequencies for solutions of I and II in C 6 D 6 is attributed to Fermi resonances. These results, in connection with the variation of n in I, are consistent with an equilibrium between monomeric and associated HgBr species for the oxobromomercuric compound I and with an intramolecularly associated monomer for the dioxomercuric compound II.