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The reaction of 3-(aryl)-2-sulfanylpropenoic acids [H 2 x spa; x : p = 3-phenyl-, f = 3-(2-furyl)-, t = 3-(2-thienyl)-] with methanol or ethanol gave the corresponding methyl (H x spme) or ethyl (H x spee) esters. The reaction of these esters (HL) with triphenyltin(IV) hydroxide gave compounds of the type [SnPh 3 L], which were isolated and characterized as solids by elemental analysis, IR spectroscopy and mass spectrometry and in solution by multinuclear ( 1 H, 13 C and 119 Sn) NMR spectroscopy. The structures of [SnPh 3 (pspme)], [SnPh 3 (fspme)] and [SnPh 3 (fspee)] were determined by X-ray diffractometry and the antimicrobial activity against E. coli , S. aureus , B. subtilis , P. aeruginosa , Resistant P. aeruginosa (a strain resistant to ‘carbapenem’), and C. albicans was tested and the in vitro cytotoxic activity against the HeLa-229, A2780 and A2780 cis cell lines was determined for all compounds. [ABSTRACT FROM AUTHOR]

The diorganolead(IV) sulfanylpropenoates [R 2 Pb(X-pspa)] {R = Me, Ph; H 2 (X-pspa) = 3-(4-X-phenyl)-2-sulfanylpropenoic acids; X = F, Cl, Br, I, CH 3 O, CF 3 O, HO} and [HQ] 2 [Ph 2 Pb(X-pspa) 2 ] (X = F, CH 3 O, HO; Q = diisopropylamine) were prepared. The structures of H 2 (Br-pspa) and [HQ] 2 [Ph 2 Pb(CH 3 O-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 [Ph 2 Pb(X-pspa)] solutions in DMSO, several compounds have been isolated and identified by X-ray diffraction. Those with [Ph 2 Pb(Cl-pspa)(DMSO)] and [Ph 2 Pb(X-pspa)(DMSO)]⋅DMSO (X = Br, CH 3 O, F 3 CO) stoichiometries consist of molecules loosely associated in dimers. However, in solid [Ph 2 Pb(HO-pspa)(DMSO)]⋅2DMSO, the [Ph 2 Pb(HO-pspa)(DMSO)] molecules are assembled in chains along the x axis. NMR and ESI-MS measurements in freshly prepared [Ph 2 Pb(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 [Me 2 Pb(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. [ABSTRACT FROM AUTHOR]

Abstract: The compound [PbPh2(NO3)2(H2O)2] was synthesized and characterized by spectroscopic methods (IR; 1H, 13C and 207Pb NMR) and mass spectrometry. An X-ray diffraction study showed that the crystal is a supramolecular tridimensional network of hydrogen-bonded PbPh2(NO3)2(H2O)2 units in which the Pb atom is octacoordinated and adopts a distorted hexagonal bipyramidal geometry, with four O (bidentate nitrate) and two O (water) atoms in equatorial positions and two C-phenyl atoms in axial positions. The crystal of [PbMe3(NO3)(H2O)], obtained as a byproduct in the synthesis of PbMe2(NO3)2, contains chains of hydrogen-bonded PbMe3(NO3)(H2O) units in which the Pb atom is pentacoordinated with a slightly distorted trigonal bipyramidal environment. In this arrangement the three C-methyl atoms are equatorial and the O atoms from the monodentate nitrate and the water molecule are axial. [Copyright &y& Elsevier]

Abstract: The interaction of dimethyl- and diethyltin(IV) cations with methylpyridoxine iodide ([MePN]I; PN = pyridoxine) was studied in ethanol/water (80:20(v/v) containing Cl−, NO3 − or I− ions in different molar ratios. Several compounds containing the deprotonated (MePN-H) or neutral (MePN) ligand were isolated and characterized by elemental analysis, IR and NMR (1H, 13C, 119Sn) spectroscopy and FAB mass spectrometry. The compounds [SnMe2(MePN-H)](I3), [SnEt2(MePN-H)](I3), [SnMe2(MePN-H)(NO3)], [SnEt2(MePN-H)(NO3)] and [SnMe2(MePN)2]I2 were studied by X-ray diffractometry. The compounds in which the MePN-H ligand is present can be described as containing dinuclear [SnR2(MePN-H)]2 2+ (R = Me, Et) units, in which two bridging chelating methylpyridoxinato ligands link two metal atoms. Interactions also exist between the metal and the I3 − or NO3 − anions and these interactions differ in degree and type. On the other hand, in the only example of a complex containing the MePN ligand, the mononuclear [SnMe2(MePN)2]2+ unit is present. The in vitro antitumor activity of these complexes against the HeLa, A2780 and A2780cis cell lines was determined and compared with that of the equivalent PN derivatives. [Copyright &y& Elsevier]

Abstract: Compounds of the type [Ag(PPh3)3(HL)] {H2 x spa=3(aryl)-2-sulfanylpropenoic acids: x = Clp [3-(2-chlorophenyl)-], -o-mp [3-(2-methoxyphenyl)-], -p-mp [3-(4-methoxyphenyl)-], -o-hp [3-(2-hydroxyphenyl)-], -p-hp [3-(4-hydroxyphenyl-); H2cpa=2-cyclopentylidene-2-sulfanylacetic acid} were synthesized and characterised by IR and NMR (1H 13C and 31P) spectroscopy and by FAB mass spectrometry. The crystal structures of [Ag(PPh3)3(HClpspa)], [Ag(PPh3)3(H-o-mpspa)], [Ag(PPh3)3(H-p-mpspa)] and [Ag(PPh3)3(Hcpa)] reveal the presence of discrete molecular units containing an intramolecular O–H···S hydrogen bond between the S atom and one of the O atoms of the COOH group. This intramolecular hydrogen bond remains in [Ag(PPh3)3(H-o-hpspa)]·EtOH and [Ag(PPh3)3(H-p-hpspa)] but in both cases polymeric structures are built on the basis of O–H···O interactions that involve the –OH substituent of the phenyl group of the sulfanylpropenoate fragment. [ABSTRACT FROM AUTHOR]

Abstract: We investigated the reaction of Pb2+, PbMe2 2+ and PbPh2 2+ with 3-(phenyl)-2-sulfanylpropenoic acid (H2pspa) to give the complexes [Pb(pspa)], [PbMe2(pspa)], [PbPh2(pspa)], [HQ]2[Pb(pspa)2] and [HQ[2[PbPh2(pspa)2] (HQ=diisopropylammonium), which were characterized by IR and NMR (1H, 13C and 207Pb) spectroscopy and by fast atom bombardment (FAB) spectrometry. The structures of [PbMe2(pspa)], [PbPh2(pspa)], [PbPh2(pspa)(dmso)]·dmso and [HQ[2[PbPh2(pspa)2] are interesting examples of unexplored Pb coordination kernels and supramolecular association. Pig renal proximal tubule LLC-PK1 culture cells were used to determine in vitro the effect of the pretreatment with H2pspa (alone or combined with vitamin B6) and [HQ]2[Zn(pspa)2] on the cytotoxicity of and by comparing the results with those of meso-2,3-dimercaptosuccinic acid (dmsa). The results show that the cell viability was scarcely affected by these agents. The ability of these reagents to decorporate lead was investigated in vivo by analysing the lead levels in the liver, kidney, brain and blood. In the case of the dimethyl derivative, and under certain protocols, undesirable effects such as an increase in brain and liver lead levels were detected. These increases were not detected when the diphenyl derivative was assayed but in this case a positive effect was not identified either. The blood lead levels also increased in the case of the dimethyl derivative and the activity of δ-ALAD was significantly recovered upon treatment with vitamin B6 or H2pspa; neither the blood lead levels nor the δ-ALAD activity was modified in the case of the diphenyl derivative. [Copyright &y& Elsevier]

Abstract: Compounds of the type [(AuPPh3)2( x spa)]; H2 x spa [ x: p =3-phenyl-, f =3-(2-furyl)-, t =3-(2-thienyl)-, -o-py =3-(2-pyridyl)-, Clp =3-(2-chlorophenyl)-, -o-mp =3-(2-methoxyphenyl)-, -p-mp =3-(4-methoxyphenyl)-, -o-hp =3-(2-hydroxyphenyl)-, -p-hp =3-(4-hydroxyphenyl)-, - diBr-o-hp =3-(3,5-dibromo-2-hydroxyphenyl)-; spa=2-sulfanyl propenoato] were synthesized and characterized by IR and NMR (1H, 13C and 31P) spectroscopy and by FAB mass spectrometry. The structures of [(AuPPh3)2(Clpspa)], [(AuPPh3)2(o-hpspa)], [(AuPPh3)2(p-hpspa)]·MeOH and [(AuPPh3)2(diBr-o-hpspa)]·2Me2CO show the dinuclear nature of the complexes with the two gold atoms, one of which is also O-bonded to an O atom of the carboxylate group, bonded to the S atom. The in vitro antitumor activities against the HeLa-229, A2780 and A2780cis cell lines were determined and the compounds were found to be highly effective, in particular against the A2780cis cell line, with eight of the nine compounds having IC50 values better than that of cisplatin. This behavior is indicative of a high ability to circumvent the cellular resistance to this drug. [Copyright &y& Elsevier]

Abstract: Compounds of the type [HQ][Au(PPh3)( x spa)] and [HP][Au(PPh3)( x spa)] {HQ=diisopropylammonium; HP=triethylammonium; H2 x spa=3-aryl-2-sulfanylpropenoic acids [ x : p =3-phenyl-, f =3-(2-furyl)-, t =3-(2-thienyl)-, -o-py =3-(2-pyridyl)-, Clp =3-(2-chlorophenyl)-, -o-mp =3-(2-methoxyphenyl)-, -p-mp =3-(4-methoxyphenyl)-, -o-hp =3-(2-hydroxyphenyl)-, -p-hp =3-(4-hydroxyphenyl)-, diBr-o-hp =3-(3,5-dibromo-2-hydroxyphenyl]} were synthesized and characterized by IR and NMR (1H, 13C and 31P) spectroscopy and by FAB mass spectrometry. The structures of [HQ][Au(PPh3)(Clpspa)] and [HQ][Au(PPh3)(-o-mpspa)] show that the crystal contains hydrogen-bonded diisopropylammonium cations and [Au(PPh3)( x spa)]− anions. The anions in the two compounds have different structures, with the carboxylate group either coordinated or not coordinated to the gold atom, respectively. The in vitro antitumour activities against the HeLa-229, A2780 and A2780cis cell lines were determined for all complexes. The diisopropylammonium derivatives were generally found to be more active, in particular against the A2780cis cell line, and showed a high ability to circumvent the cellular resistance to cisplatin. [Copyright &y& Elsevier]

Abstract: We investigated the reactions of silver nitrate with 3-(substituted phenyl)-2-sulfanylpropenoic acids H2L [L=xspa, where spa=2-sulfanylpropenoato and x∈{Clp=3-(2-chlorophenyl)-, -o-mp=3-(2-methoxyphenyl)-, -o-hp=3-(2-hydroxyphenyl)-, -p-hp=3-(4-hydroxyphenyl)-, diBr-o-hp=3-(3,5-dibromo-2-hydroxyphenyl)-}] in 1:1 and 2:1 molar ratios. The 1:1 reactions gave compounds of type [Ag(HL)], which reacted with NaOH to afford Na[Ag(L)]·xH2O (x =1 or 2) and with diisopropylamine to afford [HQ][Ag(L)] (HQ=diisopropylammonium). The 2:1 reactions gave products of type [Ag2(L)]. All the new compounds were isolated and characterized by IR spectroscopy, and all except the 2:1 adducts (which were insoluble) were studied by 1H and 13C NMR spectroscopy; ESI-MS spectrometry was also used for [HQ][Ag(L)] and Na[Ag(L)]·xH2O, and the crystal structures of H2Clpspa and [HQ][Ag(Clpspa)] were determined by X-ray diffractometry. The antimicrobial activities of the complexes against Escherichia coli, Staphylococcus aureus, Bacillus subtilis, Candida albicans, Pseudomonas aeruginosa and carbapenem-resistant P. aeruginosa were evaluated and compared with those of Ag(I) complexes with other aryl sulfanylpropenoates or related ligands. [Copyright &y& Elsevier]

Abstract: The reaction of triphenylphosphinegold(I) chloride in ethanol in a 1:1 molar ratio with the 3-(aryl)-2-sulfanylpropenoic acids H2 x spa [ x : p=3-phenyl-, Clp=3-(2-chlorophenyl)-, -o-mp=3-(2-methoxyphenyl)-, -p-mp=3-(4-methoxyphenyl)-, -o-hp=3-(2-hydroxyphenyl)-, -p-hp=3-(4-hydroxyphenyl)-, diBr-o-hp=3-(3,5-dibromo-2-hydroxyphenyl)-, f=3-(2-furyl)-, t=3-(2-thienyl)-, -o-py=3-(2-pyridyl)-; spa=2-sulfanylpropenoato] gave compounds of the type [Au(PPh3)(H x spa)], which were isolated and characterized as solids by elemental analysis, IR spectroscopy and FAB mass spectrometry and in solution by 1H, 13C and 31P NMR spectroscopy. The structures of the complexes [Au(PPh3)(HClpspa)], [Au(PPh3)(H-o-mpspa)] and [Au(PPh3)(H-p-mpspa)]·2/3C3H6O were determined by X-ray diffractometry. Hydrogen bonding was found along with Au–S and Au–P bonds in all cases and weak π–π stacking was found in the H-p-mpspa derivative. The in vitro antitumour activities against the HeLa-229, A2780 and A2780cis cell lines were determined for all complexes. [Copyright &y& Elsevier]

The reactions of dimethyl-, diethyl- and dibutyltin(IV) oxides with pyridoxine (PN) in toluene/ethanol led to the formation of compounds [SnR2(PN–2H)] which were characterized by EI and FAB mass spectrometry and by IR, Raman, Mo¨ssbauer and 1H, 13C and 119Sn NMR spectroscopy. The structures of [SnEt2(PN–2H)] · CH3OH, [SnBu2(PN–2H)] and [SnEt2(PN–2H)(DMSO)] were determined by X-ray diffractometry. The first two contain dimeric [SnR2(PN–2H)]2 units in which two bridging-chelating pyridoxinate anions link the Sn atoms, while in [SnEt2(PN–2H)(DMSO)] the DMSO coordinates to the tin atom via its O atom in a similar dimeric unit. [Copyright &y& Elsevier]

Pyridoxal 5′-phosphate (PLP) and pyridoxal (PL) itself were reacted with diorganotin(IV) derivatives in the presence and absence of aminoacids. With PLP the complexes [SnR2(PLP-2H)] (R=Me, Et, Bu) were isolated and characterized by EI and FAB mass spectrometry and by IR, Raman and Mo¨ssbauer spectroscopy. Reaction mixtures containing PL, valine or glycine and SnR2(OAc)2 (R=Me, Et) afforded complexes of the form [SnR2(PLPM-2H)], where PLPM is the Schiff base formed by condensation of PL and pyridoxamine (PM). PM was presumably formed by transamination between valine or glycine and PL. The PLPM complexes, and their butyl and phenyl analogues, were also synthesized directly by reacting SnR2O and PLPM, and were characterized by EI and FAB MS, by IR, Raman, Mo¨ssbauer and NMR spectroscopy, and in the case of the methyl and ethyl compounds by single-crystal X-ray diffractometry. Crystals of [SnMe2(PLPM-2H)]·H2O and [SnEt2(PLPM-2H)] consist of molecules in which the ligand is bound to the metal through the O atoms of the two deprotonated phenolic hydroxyl groups and the iminic N atom, and the metal exhibits distorted square pyramidal coordination. Both PLPM and its complexes show intense antibacterial activity against Pseudomonas aeruginosa (ATCC27853), but only the complexes exhibit significant activity against the other four bacterial strains assayed, Staphylococcus aureus, Bacillus subtilis, Escherichia coli and a carbapenem-resistant P. aeruginosa strain. [Copyright &y& Elsevier]

Hydrogen bonded water–halide {[(H2O)4X2]2−}n tapes have been identified in the complexes [SnMe2(MePN–H)]Cl·2H2O and [SnMe2(MePN–H)]Br·2H2O where MePN is N-methylpyridoxine (PN=pyridoxine, vitamin B6). The tape can be described as planar (H2O)4 units linked by two chloride/bromide anions creating a stair-case like architecture. In the two isostructural crystals dinuclear [SnMe2(MePN–H)]22+ units are hydrogen bonded to the X− anion of the tape via the C(5)一CH2OH fragment of the pyridoxine ligand. There is no significant interaction between the cations, which supports the organizing character of the water–halide tape. [Copyright &y& Elsevier]