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O Crespo

Publications and source records attributed to O Crespo.

12 recordsLinked to original sources

Ability of a Au(III)-N unit to bond two aurophilically interacting gold(I) centers.

The monohapto neutral 2-(diphenylphosphino)aniline (PNH(2)) complexes [Au(C(6)F(5))(2)X(PNH(2))] (X = C(6)F(5) (1), Cl (2)) have been obtained from [Au(C(6)F(5))(3)(tht)] or [Au(C(6)F(5))(2)(micro-Cl)](2) and PNH(2), and the cationic [Au(C(6)F(5))(2)(PNH(2))]ClO(4) (3) has been similarly prepared from [Au(C(6)F(5))(2)(OEt(2))(2)]ClO(4) and PNH(2) or from 2 and AgClO(4). The neutral amido complex [Au(C(6)F(5))(2)(PNH)] (4) can be obtained by deprotonation of 3 with PPN(acac) (acac = acetylacetonate) or by treatment of the chloro complex 2 with Tl(acac). It reacts with [Ag(OClO(3))(PPh(3))] or [Au(OClO(3))(PPh(3))] to give the dinuclear species [Au(C(6)F(5))(2)[PNH(MPPh(3))]]ClO(4) (M = Ag (5), Au (6)). The latter can also be obtained by reaction of equimolar amounts of 3 and [Au(acac)(PPh(3))]; when the molar ratio of the same reagents is 1:2, the trinuclear cationic complex [Au(C(6)F(5))(2)[PN(AuPPh(3))(2)]]ClO(4) (7) is obtained. The crystal structures of complexes 2-4 and 7 have been established by X-ray crystallography; the last-mentioned displays an unusual Au(I)-Au(III) interaction.

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Helicobacter pylori vacA genotypes, cagA status and ureA-B polymorphism in isolates recovered from an Argentine population.

Several reports have evidenced geographic differences in the prevalence of vacA (vacuolating cytotoxin gene) alleles and cagA (cytotoxin-associated gene) status among Helicobacter pylori isolates. We investigated the occurrence of these virulence-associated genes status among our isolates, and their relationship with ulcer disease outcome. Besides, ureA-B polymorphism was studied. One hundred isolates, comprising 32 from patients with ulcer disease (UD) and 68 from patients with non-ulcer dyspepsia (NUD), were analyzed. Eighty-four percent of isolates were cagA-positive without statistically significant difference in prevalence between patients with UD or NUD. Genotype vacA-s1m1 was predominant, although unlike other South American regions, subtype s1am1 occurrence was higher than s1b. The multivariate model used to estimate the predictive value of cagA and vacA status for UD development disclosed infection with vacA-s1am1 isolates as the only variable that increased the risk of UD onset. ureAB fingerprinting showed considerable genetic divergence among isolates, however, confirmed that certain DNA banding profiles are conserved worldwide.

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Heteropolynuclear phosphide complexes: phosphorus as unique atom bridging coinage metal centres.

In this paper we describe the synthesis and reactivity of the diphenylphosphine derivatives [Au(C6F5)(PPh2H)] and trans-[Au(C6F5)2(PPh2H)2]ClO4. Reactions of the latter or the neutral [Au(C6F5)3(PPh2H)] with the appropriate Group 11 metal reagents (M = Au, Ag, Cu) in the presence of acetylacetonate afford a series of novel Au(III)-M phosphido-bridged complexes, which have been scarcely represented to date. The crystal structure of the tetranuclear [(Au(C6F5)2(mu-PPh2)2Ag)2] and the dinuclear [Au(C6F5)3(mu-PPh2)M(PPh3)] (M = Au,Ag) complexes were established by X-ray diffraction methods. The synthesis and deprotonating activity of the anionic gold(III) complex PPN[Au(C6F5)3(acac)] (PNN = [N(PPh3)2]+) was studied.

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Experimental and theoretical studies of the d8-d10 interaction between Pd(II) and Au(I): bis(chloro[(phenylthiomethyl)diphenylphosphine]gold(I))- dichloropalladium(II) and related systems.

The reaction between thioether phosphine gold(I) precursors such as [AuCl(Ph2PCH2SPh)], 1, or [Au(Ph2PCH2SPh)2]CF3SO3 and PdCl2(NCPh)2 affords the new compounds [(AuCl(Ph2PCH2SPh)2PdCl2], 2, and [AuPdCl2(Ph2PCH2SPh)2]CF3SO3, 3. The crystal structure of complex 2 has the sterically unhindered Pd(II) and Au(I) at a distance of 314 pm. Quasirelativistic pseudopotential calculations on [AuPdCl3(PH2CH2SH)(SH2)] models give short Au-Pd distances at the second-order Møller-Plesset (MP2) level and long Au-Pd distances at Hartree-Fock (HF) level. A detailed analysis of the Au-Pd interaction shows dominant dispersion, some ionic contributions, and no net charge transfer between the metals.

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Synthesis, structure, luminescence, and theoretical studies of tetranuclear gold clusters with phosphinocarborane ligands.

Treatment of the tetranuclear gold cluster [Au4((PPh2)2C2B9H10)2(AsPh3)2] (1), which contains the nido-carborane-diphosphine [7,8-(PPh2)2C2B9H10]-, with various tertiary phosphines leads to derivatives [Au4((PPh2)2C2B9H10)2-(PR3)2] (PR3 = PPh3 (2), P(4-MeC6H4)3 (3), P(4-OMeC6H4)3 (4)). The X-ray crystal structure of complex 4 shows a tetrahedral framework of gold atoms, two of which are chelated by the diphosphine, and two are coordinated to one monophosphine ligand each. These compounds are very stable and are obtained in high yield. MP2 calculations suggest that the two types of chemically nonequivalent gold atoms can be formally assigned as Au(I) (those attached to the arsines or phosphines) and Au(0) (those bonded to the anionic diphosphine) and emphasize the role of correlation in the gold-gold interactions. The compounds are luminescent. The emission is assigned to a gold-centered spin-forbidden transition; the assignment of the oxidation state of the gold centers on this basis leads to results coincident with those obtained by theoretical calculations.

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Gold and silver complexes with the ferrocenyl phosphine FcCH2PPh2.

Linear gold(I) and silver(I) complexes with the ferrocenyl phosphine FcCH2PPh2 [Fc = (eta5-C5H5)Fe(eta5-C5H4)] of the types [AuR(PPh2CH2Fc)], [M(PPh3)(PPh2CH2Fc)]OTf, and [M(PPh2CH2Fc)2]OTf (M = Au, Ag) have been obtained. Three-coordinate gold(I) and silver(I) derivatives of the types [AuCl(PPh2CH2Fc)2] and [M(PPh2CH2Fc)3]X (M = Au, X = ClO4; M = Ag, X = OTf) have been obtained from the corresponding gold and silver precursors in the appropriate molar ratio, although some of them are involved in equilibria in solution. The crystal structures of [AuR(PPh2CH2Fc)] (R = Cl, C6F5), [AuL(PPh2CH2Fc)]OTf (L = PPh3, FcCH2PPh2), [Au(C6F5)3(PPh2CH2Fc)], and [Ag(PPh2CH2Fc)3]OTf have been determined by X-ray diffraction studies.

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Heteropolynuclear complexes with the ligand Ph2PCH2SPh: theoretical evidence for metallophilic Au-M attractions

Addition of two equivalents of diphenylthiomethylphosphine (PPh2-CH2SPh) to the starting materials [Au(tht)2]A (tht = tetrahydrothiophene), AgCF3SO3, or [Cu(CH3CN)4]CF3SO3 produces the mononuclear derivatives [M(PPh2CH2SPh)2]A (M = Au, A = CF3SO3 (1a); M = Au, A = ClO4 (1b); M = Ag, A = CF3SO3 (4); M = Cu, A = CF3SO3 (5)) which are able to form the heterodinuclear complexes [AuM'(PPh2CH2SPh)2](CF3SO3)2 (M' = Ag (2), Cu (3)) with a P-Au-P environment. If the starting gold complex is [Au(C6F5)(tht)], reaction with the phosphine produces [Au(C6F5)-(PPh2CH2SPh)] (6) from which, by reaction with AgCF3SO3 or [Cu(CH3CN)4]CF3SO3, the "snake"-type linear complexes [Au2M(C6F5)2-(PPh2CH2SPh)2]CF3SO3 (M = Ag (7), Cu (8)) are obtained. If the silver starting complex is AgCF3CO2, reaction in a 1:1 ratio gives the tetranuclear complex [Au2Ag2(C6F5)2(PPh2CH2SPh)2-(CF3CO2)2] (9). When the molar ratio is 1:2 the trinuclear complex [AuAg2(C6F5) (CF3CO2)2(PPh2CH2SPh)] (10) is obtained. According to ab initio calculations, the presence of only one gold atom is enough to induce metallophilic attractions in the group congeners, and this effect can be modulated depending on the gold ligand.

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Solvent-free

The title compound, [Au(2)Cl(2)Fe(C(17)H(14)P)(2)], (I), contains the expected linear gold centres. The ferrocene moiety acts as a P, P'-bridging ligand, wherein the Fe atom lies on an inversion centre. The P-Au-Cl angle is 177.56 (8) degrees and bond distances Au-P and Au-Cl are 2.2261 (18) and 2.2781 (18) A, respectively. The structure is almost identical to that of the metal complex in (I).2CH(2)Cl(2) [Canales, Gimeno, Jones, Laguna & Sarroca (1997). Inorg. Chem. 36, 5206-5211], but differs considerably from that in 3(I).2CHCl(3) [Hill, Girard, McCabe, Johnson, Stupik, Zhang, Reiff & Eggleston (1989). Inorg. Chem. 28, 3529-3533], in that in the latter, the two independent molecules are linked by a short Au.Au contact.

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7-diphenyl

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