Ezequiel M. Vázquez López

A novel hexanuclear silver(I) cluster containing a regular Ag6 ring with short Ag–Ag distances and an argentophilic interaction

The hexanuclear complex [HQ][Ag(p-mpspa)] (H2-p-mpspa = 3-(4-methoxyphenyl)-2-sulfanylpropenoic acid) was prepared by reacting the precursor [Ag(H-p-mpspa)] with diisopropylamine (Q). The complex was characterized by spectroscopic techniques and the structure was solved by a single crystal X-ray diffraction study. The crystal contains hydrogen-bonded diisopropylammonium cations and [Ag6(p-mpspa)6](6-) anions that are based on a regular Ag6 ring with each S-donor atom of the sulfanylcarboxylate ligand bridging two Ag atoms. The Ag-Ag bond distances, 2.8036(6) Å, are very short and suggest a closed shell d(10)···d(10) argentophilic interaction. To analyze the relative role of this interaction and that of the S-bridging atom the anionic [Ag6(p-mpspa)6](6-) moiety has been studied theoretically at the Hartree-Fock (HF) and 2(nd) order Møller-Plesset perturbation theory (MP2) levels on a very simple [Ag6(SH)6] A model system. A large model system [Ag6(p-mpspa)6](6-)B has also been studied by applying the ONIOM (QM/MM) approach using HF/UFF and MP2/UFF combinations as levels of theory. The six experimentally observed Ag(I)···Ag(I) supported interactions are reproduced when dispersion-type interactions are considered in the theory levels MP2 and ONIOM MP2/UFF for models A and B, respectively. The use of HF and ONIOM HF/UFF levels led to a similar hexanuclear structure but displayed a large hexagonal disposition without argentophilic contacts for both models A and B. The steric hindrance exerted by the ligands did not preclude the formation of argentophilic interactions, as observed experimentally.

Organotin(IV) complexes of 4,6-dimethylpyrimidine-2-thione, Me2PymtH. Preparation, characterization and crystal structure determination of cis-[Ph2Sn(Me2Pymt)2] and [Ph3Sn(Me2Pymt)]

Abstract The coordination mode of the ambidentate ligand 4,6-dimethylpyrimidine-2-thione (Me2PymtH) was investigated with respect to the organotin(IV) compounds, namely Me2SnCl2, n-Bu2SnCl2, Ph2SnCl2 and Ph3SnCl. An X-ray crystal structure determination carried out on cis-[Ph2Sn(Me2Pymt)] (3) and [Ph3Sn(Me2Pymt)] (4) revealed that the Me2Pymt− ligand is N,S-coordinated in both complexes. The Sn(IV) atom is six-coordinated in 3 and five-coordinated in 4. The similarities observed in the IR, NMR (1H, 13C) and mass spectroscopy are indicative of a similar behavior of the ligand in all the complexes, thus suggesting a six-coordination in the dimethyltin (1) derivative and five-coordination in the dibutyltin (2) one. The complexes were characterized by means of elemental analysis, IR, NMR (1H, 13C) and mass spectroscopic methods.

Dinuclear triphenylphosphinegold(I) sulfanylcarboxylates: Synthesis, structure and cytotoxic activity against cancer cell lines.

Compounds of the type [(AuPPh(3))(2)(xspa)]; H(2)xspa [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 ((1)H, (13)C and (31)P) spectroscopy and by FAB mass spectrometry. The structures of [(AuPPh(3))(2)(Clpspa)], [(AuPPh(3))(2)(o-hpspa)], [(AuPPh(3))(2)(p-hpspa)].MeOH and [(AuPPh(3))(2)(diBr-o-hpspa)].2Me(2)CO 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 IC(50) values better than that of cisplatin. This behavior is indicative of a high ability to circumvent the cellular resistance to this drug.

Synthesis, Structural Characterization, and Antiinflammatory Activity of Triethylphosphinegold(I) Sulfanylpropenoates of the Type [(AuPEt3)2xspa] [H2xspa = 3-(Aryl)-2-sulfanylpropenoic acid] : an (H2O)6 Cluster in the Lattice of the Complexes [(AuPEt3)2xspa] ·3H2O

Gold complexes of the type [(AuPEt3)2xspa] were prepared by reacting AuPEt3Cl in basic media with the 3-(aryl)-2-sulfanylpropenoic acids H2xspa [x = p, Clp, -o-mp, -p-mp, -o-hp, -p-hp, diBr-o-hp, f, t, -o-py; 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], and 2-cyclopentylidene-2-sulfanylacetic acid (H2cpa). The complexes were characterized by spectroscopic methods (IR, (1)H, (13)C and (31)P NMR) and mass spectrometry, and the complexes [(AuPEt3)2pspa] x 3 H2O, [(AuPEt3)2-p-hpspa] x 3 H2O, [(AuPEt3)2tspa)] x 3 H2O, and [(AuPEt3)2-o-hpspa] by X-ray diffractometry. The crystals of the first three complexes contain (H2O)6 clusters hydrogen bonded to [(AuPEt3)2xspa]2 dimer units, whereas in the -o-hpspa derivative the hydrogen bonds are between the monomer [(AuPEt3)2-o-hpspa] units. The antiinflammatory activity of the complexes against plantar edema induced by carrageenan in rats is generally significant, with the values for the o-hpspa and tspa derivatives being particularly high.

Synthesis, structure and cytotoxicity studies of diisopropylammonium and triethylammonium salts of triphenylphosphinegold(I) sulfanylcarboxylates

Compounds of the type [HQ][Au(PPh(3))(xspa)] and [HP][Au(PPh(3))(xspa)] {HQ=diisopropylammonium; HP=triethylammonium; H(2)xspa=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 ((1)H, (13)C and (31)P) spectroscopy and by FAB mass spectrometry. The structures of [HQ][Au(PPh(3))(Clpspa)] and [HQ][Au(PPh(3))(-o-mpspa)] show that the crystal contains hydrogen-bonded diisopropylammonium cations and [Au(PPh(3))(xspa)](-) 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.

Phenylmercury(ii) sulfanylpropenoates: an example of symmetrization with the 3-(2-methoxyphenyl)-2-sulfanylpropenoato ligand

We investigated the reactions of phenylmercury(II) acetate with 3-(substituted phenyl)-2-sulfanylpropenoic acids H2L [L = xspa, where spa = 2-sulfanylpropenoato and x ∈ {o-mp = 3-(2-methoxyphenyl)-}, p-mp = 3-(4-methoxyphenyl)-, o-tfmp = 3-(2-trifluoromethoxyphenyl)-, p-tfmp = 3-(4-trifluoromethoxyphenyl)-] in the presence of diisopropylamine in ethanol. The 1:1:1 reactions gave compounds of type [HQ][PhHg(L)] [where HQ = diisopropylammonium cation]. All the new compounds were isolated and characterized by elemental analysis, FAB mass spectrometry and IR, and NMR (1H, 13C, 199Hg) spectroscopy. The crystal structures of the [HQ][PhHg(L)] compounds show the presence of diisopropylammonium cations and [PhHg(L)]− anions, in which the Hg atom adopts a HgCOS distorted T-environment. For the o-mpspa derivative, a symmetrization process, followed in solution by NMR spectroscopy, was detected and crystals of [HQ][PhHg(o-mpspa)]·0.5HgPh2 were isolated and studied by X-ray diffraction.