Aránzazu Mendía

Synthesis, Characterization, and in Vitro Cytotoxicity of Some Gold(I) and Trans Platinum(II) Thionate Complexes Containing Water-Soluble PTA and DAPTA Ligands. X-ray Crystal Structures of [Au(SC4H3N2)(PTA)], trans-[Pt(SC4H3N2)2(PTA)2], trans-[Pt(SC5H4N)2(PTA)2], and trans-[Pt(SC5H4N)2(DAPTA)2]

A series of gold(I) and platinum(II) complexes of the type [Au(SR)(P)] and trans-[Pt(SR) 2(P) 2] [SR = 2-thiopyridine (SPy), 2-thiopyrimidine (SPyrim); P = 1,3,5-triaza-7-phosphaadamantane (PTA), 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA)] were prepared and characterized, and their in vitro cytotoxicities against a panel of seven human cancer cell lines were evaluated. The highly water soluble gold(I) complexes [Au(SR)(P)] [P = PTA and SR = SPy ( 1), SPyrim ( 2); P = DAPTA and SR = SPy ( 3), SPyrim ( 4)] showed low cytotoxicity, while the platinum(II) complexes trans-[Pt(SR) 2(P) 2] [P = PTA and SR = SPyrim ( 5), SPy ( 6); P = DAPTA and SR = SPyrim ( 7), SPy ( 8)] demonstrated potent cytotoxicity for ovarian, colon, renal, and melanoma cancer cell lines on the basis of a comparison with ID 50 values for some established cytotoxic drugs. Single crystals of 2, 5, 6, and 8 suitable for X-ray structural characterization were obtained, and the study revealed the trans configuration for 5, 6, and 8 in their solid states.

(Polyhalophenyl)silver(I) complexes as arylating agents: Crystal structure of [(μ-2,4,6-C6F3H2)(AuPPh3)2]ClO4

Abstract The arylsilver derivatives AgR (R = C6F5, 2,4,6-C6F3H2 or C6Cl5) react with chlorogold(I) precursors [AuCl(tht), AuCl(PPh3), ClAu(dppm)AuCl (tht = tetrahydrothiophene, dppm = bis(diphenylphosphino)methane], to give the corresponding arylgold complexes in good yield. With gold precursors in higher oxidation state, AgC6Cl5 either causes reduction to gold(I) or gives no reaction, whereas AgC6F5 and AgC6F3H2 lead to gold(II) complexes (R2Au(dppm)AuR2) or gold (III) complexes [Au(C6F3H2)(C6F5)2(PPh3); Au(C6F3H2)2(C6F5)(tht); Au(C6F5)3(tht); Au(C6F3H2)3(tht)].

trans-Thionate Derivatives of Pt(II) and Pd(II) with Water-Soluble Phosphane PTA and DAPTA Ligands: Antiproliferative Activity against Human Ovarian Cancer Cell Lines

A series of PTA and DAPTA platinum(II) and palladium(II) thionate complexes of the type trans-[M(SN)2P2] were prepared from the reaction of cis-[MCl2P2] [M = Pt, Pd; P = PTA (1,3,5-triaza-7-phosphaadamantane), DAPTA (3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane)] with the in situ generated sodium salts of the heterocyclic thiones S-m-methylpyrimidine-2-thione, S-4,6-dimethylpyrimidine-2-thione, S-4,6-dihydroxypyrimidine-2-thione, benzothiazole-2-thione, benzoxazole-2-thione, S-1,3,4,-thiadiazole-2-thione, S-4,5-H-thiazolan-2-thione, and S-pyrimidine-4(1H)-one-2-thione. The X-ray structures of six of the compounds confirm the trans disposition and, only in the case of [Pd2Cl2(S-pyrimidine-4(1H)-one-2-thionate)2(PTA)2], a dinuclear structure with a Pd-Pd distance of 3.0265(14)Å was observed. In vitro cytotoxicities against human ovarian cancer cell lines A2780 and A2780cisR were evaluated for ten complexes showing a high inhibition of cellular growth with a comparable inhibitory potency (IC50) against A2780 cells to that of cisplatin. Notably, the compounds also show significant (up to 7-fold higher) activity in cisplatin-resistant A2780cisR cell lines.

Pyridine-2-thionate as a versatile ligand in Pd(II) and Pt(II) chemistry: the presence of three different co-ordination modes in [Pd2(μ2-S,N-C5H4SN)(μ2-κ2S-C5H4SN)(μ2-dppm)(S-C5H4SN)2]

Reactions of [MCl2(L-L)], M = Pt, Pd; L-L = bis(diphenylphosphino)methane (dppm) or bis(diphenylphosphino)ethane (dppe), with NaC5H4SN in a 1 : 2 molar ratio lead to mononuclear species [M(S-C5H4SN)2(P-P)], M = Pt; L-L = dppm (1) or dppe (2) and M = Pd; L-L = dppe (3), as well as to the dinuclear [Pd2(micro2-S,N-C5H4SN)(micro2-kappa2S-C5H4SN)(micro2-dppm)(S-C5H4SN)2] (4). In contrast, reaction of [MCl2(dppm)] with NaC5H4SN in a 1 : 1 molar ratio leads to [Pd2(micro2-S,N-C5H4SN)3(micro2-dppm)]Cl (5) and trans-[Pt(S-C5H4SN)2(PPh2Me)2] (6) respectively. The latter is formed in low yield by cleavage of the dppm ligand. The dinuclear derivatives 4 and 5 present an A-frame and lantern structure, respectively. The former showing three different co-ordination modes in the same molecule with a short Pd-Pd distance of 2.9583 (9) A and the latter with three bridging S,N thionate ligands showing a shorter Pd-Pd distance of 2.7291 (13) A. Both distances could be imposed by the bridging ligands or point to some sort of metal-metal interaction.

Unexpected diastereoisomeric-trimers in the crystalline structure of triflatetriphenylphosphinesilver(I)

Abstract The synthesis and spectroscopic properties of [Ag3(O3SCF3)3(PR3)3] (PR3=PPh3 and PPh2Me) are described and the trimeric nature has been confirmed in the case of the PPh3 derivative. The X-ray crystal structure of [Ag3(O3SCF3)3(PPh3)3] shows that each triflate group is in a different coordination mode and that there are two diastereoisomers in the asymmetric unit.

Reactions of thallium(III) chloride with (aryl)silver(I) complexes. Crystal structure of [Tl(mes)2][TlCl3(mes)] (mes = mesityl)

Abstract The arylsilver derivatives AgR (R = mesityl, C6F3H2, C6F5) react with TlCl3 to give arylthallium(III) complexes of the types [TlR2][TlCl3R], TlClR2 or TlR3. The structure of [Tl(mes)2][TlCl3(mes)] has been established by X-ray crystallography; it consists of linear [Tl(mes)2]+ cations and tetrahedral [TlCl3(mes)]− anions, linked into chains by additional weak Tl…Cl interactions.

Four- five- and six-co-ordinated pentafluorophenylthallium(III) complexes.: Crystal structures of [Tl(C6F5)3(OPPh3)], [Tl(C6F5)2Cl(OPPh3)]2 and [Tl(C6F5)2(OdppmO)2][Tl(C6F5)2Cl2]

[NBu 4 ][Ag(C 6 F 5 ) 2 ] or [Ag(C 6 F 5 )] act as arylating ligands able to transfer two or one pentafluorophenyl groups to [Tl(C 6 F 5 ) 2 Cl] leading to [NBu 4 ][Tl(C 6 F 5 ) 4 ] ( 1 ) and [Tl(C 6 F 5 ) 3 (diox)] (diox=1,4 dioxane) ( 2 ) in an improved synthesis, the latter being a starting material for the synthesis of [Tl(C 6 F 5 ) 3 (OPPh 3 )] ( 3 ) and [Tl(C 6 F 5 ) 3 (PPh 3 )] ( 4 ). However, [Ag(C 6 F 5 )L] does not transfer the pentafluorophenyl group when reacted with [Tl(C 6 F 5 ) 2 Cl] and the complexes [Tl(C 6 F 5 ) 2 Cl(py)] 2 ( 5 ), [Tl(C 6 F 5 ) 2 Cl(OPPh 3 )] 2 ( 6 ) and [Tl(C 6 F 5 ) 2 (OdppmO) 2 ][Tl(C 6 F 5 ) 2 Cl 2 ] ( 7 ) are obtained as the main products, which can be obtained in a better yield by the addition of the neutral ligands to [Tl(C 6 F 5 ) 2 Cl]. The X-ray structure of complexes 3 , 6 and 7 show thallium(III) centres in a tetrahedral, trigonal bipyramidal or octahedral arrangements, respectively.

[Tl(OPPh3)2][Au(C6F5)2]: the first extended unsupported gold–thallium linear chain

Li[Au(C6F5)2] reacts with TlNO3 in the presence of OPPh3 affording a complex of stoichiometry [AuTl(C6F5)2- (OPPh3)2]n, which presents different luminescence properties depending on the conditions and whose crystal structure reveals the existence of unsupported Au–Tl bonds forming a polymeric linear chain.