New diorganolead(IV) sulfanylpropenoates: Synthesis, characterization and analysis of their evolution in DMSO solution

作者：Casas Jose S^*; Victoria Castano M; Couce Maria D; Sanchez Agustin; Sordo Jose; Dolores Torres M; Vazquez Lopez Ezequiel M

来源：Journal of Organometallic Chemistry, 2015, 789-790: 29-39.

DOI：10.1016/j.jorganchem.2015.04.036

• Organolead(IV)sulfanylpropenoates
• X-ray structures
• PD150606
• ESI-TOF
• NMR

The diorganolead(IV) sulfanylpropenoates [R2Pb(X-pspa)] {R = Me, Ph; H-2(X-pspa) = 3-(4-X-phenyl)-2-sulfanylpropenoic acids; X = F, Cl, Br, I, CH3O, CF3O, HO} and [HQ](2)[Ph2Pb(X-pspa)(2)] (X = F, CH3O, HO; Q = diisopropylamine) were prepared. The structures of H-2(Br-pspa) and [HQ](2)[Ph2Pb(CH3O-pspa)(2)], 2H(2)O were fully characterized in the solid state using X-ray diffraction.
All sulfanylpropenoates and free sulfanylpropenoic acids are fairly soluble in DMSO. The acids are in general oxidised to the corresponding disulfide by DMSO except H-2(I-pspa), a selective calpain inhibitor, which evolves to form two decomposition products neither of which is probably the disulfide. From the [Ph2Pb(X-pspa)] solutions in DMSO, several compounds have been isolated and identified by X-ray diffraction. Those with [Ph2Pb(Cl-pspa)(DMSO)] and [Ph2Pb(X-pspa)(DMSO)]center dot DMSO (X = Br, CH3O, F3CO) stoichiometries consist of molecules loosely associated in dimers. However, in solid [Ph2Pb(HO-pspa)(DMSO)]center dot 2DMSO, the [Ph2Pb(HO-pspa)(DMSO)] molecules are assembled in chains along the x axis. NMR and ESI-MS measurements in freshly prepared [Ph2Pb(X-pspa)] solutions are compatible with the presence of dimeric or polymeric species such as those isolated in the solid state. However, the NMR spectra of [Me2Pb(X-pspa)] revealed that these compounds decompose quickly in DMSO due to redistribution reactions suffered by the organometallic moiety and the concomitant partial decomposition of the sulfanylpropenoates.

• 出版日期2015-8-1