Experimental and theoretical evidence of the first Au(I)Bi(III) interaction

3 pages, 3 figures, 1 scheme.-- Published as an advance article on the web 15th Nov. 2006.Complex [Au(C6F5)2][Bi(C6H4CH2NMe2-2)2] 1 displays the first example of an interaction between Au(I) and Bi(III), the nature of which is shown to be consistent with the presence of a high ionic contribution (79%) and a dispersion type (van der Waals) interaction (21%).The D.G.I.(MEC)/FEDER (CTQ2004-05495) project is acknowledged. M. Monge thanks the MEC-UR for his contract ‘‘Ramón y Cajal’’. EC through the Socrates/Erasmus program (M. Nema) and a NATO research fellowship (C. Silvestru) are also acknowledged.Peer reviewe

Luminescent gold–silver complexes derived from neutral bis(perfluoroaryl)diphosphine gold(I) precursors

Complex [Au{4-C6F4(4-C6BrF4)}(tht)] reacts with diphosphines (L–L) such as bis(diphenylphosphino)methane (dppm) or 1,2-bis(diphenylphosphino)benzene (dppb) in a 2 : 1 molar ratio in dichloromethane, leading to neutral products of stoichiometry [(Au{4-C6F4(4-C6BrF4)})2(μ-L–L)] (L–L = dppm (1), dppb (2)). In the crystal structure of complex 2 short Au⋯Au interactions of 2.9367(5) and 2.9521(5) Å appear. This complex displays an orange emission, which is assigned to arise from a charge transfer transition from a metal centered Au–Au orbital to an orbital located at the diphosphine ligand. Addition of silver trifluoroacetate to these complexes in a 1 : 1 or a 2 : 1 molar ratio generates polymeric heterometallic gold–silver compounds of stoichiometry [Ag2Au2{4-C6F4(4-C6BrF4)}2(CF3CO2)2(μ-L–L)]n (L–L = dppm (3), dppb (4)), which confirms the capability of the neutral [(Au{4-C6F4(4-C6BrF4)})2(μ-diphosphine)] units to act as electron density donors when treated with a Lewis acid substrate. These heterometallic derivatives show blue emissions indicating large HOMO–LUMO band gaps, due to the stabilization that the gold-based HOMO orbitals suffer when the electron withdrawing silver trifluoroacetate fragments interact with them

Comparación entre las técnicas de cribado de patología cervical y las conizaciones de tres hospitales en españa

Objetivo: Analizar las características poblacionales y los métodos diagnósticos de patología cervical para la prevención del cáncer de cérvix de tres hospitales españoles para mejorar y unificar los programas de cribado y prevención. Material y métodos: Estudio retrospectivo de las características demográficas y clínicas de 408 mujeres con patología cervical uterina diagnosticadas en 3 hospitales españoles. Se comparan los factores de riesgo, el proceso diagnóstico y la indicación de tratamiento de dos grupos: las que requirieron conización cervical (n=222) y las que no precisaron tratamiento quirúrgico (n=186). También se analizan las recomendaciones vacunales y su grado de cumplimiento. Resultados: Las mujeres conizadas usaron más anticoncepción hormonal y tienen un mayor hábito tabáquico mientras que el número de compañeros sexuales es mayor en pacientes no conizadas. Más del 50% de pacientes con biopsia cervical positiva presentaron un resultado igual o más grave en la anatomía patológica de la pieza quirúrgica. Existen diferencias significativas en sensibilidad y valor predictivo positivo de la citología y de la determinación de HPV entre hospitales. La recomendación de vacunación en ambos grupos fue similar, el porcentaje de mujeres que no la cumplieron fue elevado y significativamente mayor entre pacientes conizadas. Conclusión: En nuestro medio las mujeres conizadas tienen características clínicas y epidemiológicas diferentes a las no conizadas, existen diferencias entre las técnicas diagnósticas de distintos hospitales y sin embargo la concordancia entre biopsia y resultado del cono es elevada. Sigue siendo necesaria una correcta educación sanitaria en relación con la vacunación en mujeres con patología cervical. Background: To analyse the characteristics of the population and diagnostic methods related to the cervical cancer prevention program in three different-level hospitals of a Spanish region in order to improve and unify the screening program. Methods: We retrospectively studied demographic and clinical characteristics of 408 women with cervical lesions diagnosed in three hospitals in Aragon (Spain). Correlation between risk factors, diagnosis process and conisation indication was analysed divided in two groups: conisation required (n=222) or non-conisation (n=186). We also assessed the number of vaccine recommendations made to the patients and the degree of compliance. Results: Conisaited women more frequently used a combined hormonal contraceptive method and are more smokers, while the sexual partners are more in women without conisation. More than 50% of women con positive biopsy was confirmed after surgical treatment. There are significant differences between sensibility and positive predictive value of pap-smear and HPV determination in different hospitals. The recombinant vaccine was recommended to both groups at a similar rate. The percentage of women who were recommended to receive the vaccine but chose not to do it, was high in both groups but significantly higher in the Conisation group. Conclusion: In our environment conisaited women have different clinical and epidemiological profiles, there are differences between diagnosis techniques in different hospitals, however, the concordance between biopsy and definitive result is high. A good sanitary education is necessary in relation with the vaccination of women with cervical pathology

Mixed-Valent Linear Chains of Gold Atoms. X-Ray Structure of [{(2,4,6-C6F3H2)Au(CH2PPh2CH2)2Au}2Au(CH2PPh2CH2)2Au](ClO4)2

Reactions of asymmetrical gold(II) derivatives [RAu(CH2PPh2CH2)2AuX] (R = C6F5, 2,4,6-C6F3H2; CH3, X = halogen) with AgClO4 lead to the compounds [RAu(CH2PPh2CH2)2AuOClO 3], which further react with NBu4[AuR2] (R = C6F5, C6F3H2) or [Au(CH2PPh2CH2)2Au] to give pentanuclear [{RAu(CH2PPh2CH2)2Au} 2AuR2]ClO4 or hexanuclear [{RAu(CH2PPh2CH2)2-Au} 2Au(CH2PPh2CH2) 2Au](ClO4)2 gold complexes in different oxidation states. The same results can be achieved if the reactions are carried out with [RAu(CH2PPh2CH2)2Au(tht)]ClO 4 (tht = tetrahydrothiophene). The structure of [{(2,4,6-C6F3H2)Au(CH2PPh 2CH2)2Au}2Au(CH2PPh 2-CH2)2Au](ClO4)2 has been determined by a single-crystal X-ray diffraction study. It crystallizes in the monoclinic space group P21/c with a = 12.150(1) Å, b = 15.498(2) Å, c = 24.693(2) Å, = 95.18(1)°, Z = 2, R = 0.0404, and Rw = 0.0417 for 5132 observed reflections. The centrosymmetric cationic complex exhibits a linear hexametallic skeleton and is composed of three pairs of gold atoms, each of them doubly bridged by two bis-ylide ligands. Two -bonded C6F3H2 groups complete the coordination of the external gold centers. The three "Au(CH2PPh2CH2)2Au" moieties are held together through two unbridged Au-Au direct bonds (2.7370(7) Å), with the ligand-bridged Au-Au separations at 2.6540(7) and 2.8378(7) Å. 1994 American Chemical Society

Synthesis and structure of [M(CO)4{(PPh2)2CHAu(PPh3)}] (M = Cr, Mo, W)

The reaction of diethyl ether solutions of Li[M(CO)4{(PPh2)2CH}] with [AuCl(PPh3)] gives [M(CO)4{(PPh2)2CHAu(PPh3)}] (M = Cr, Mo, W). The structure of the derivative with M = Mo was determined by single-crystal X-ray diffraction at 173 K. Crystals are monoclinic, space group P22, a = 13.552(3), b = 17.390(4), c = 17.390(4) A , = 90.94(2)°, Z = 4 and R(F) = 0.031. The two independent molecules are very similar. The molybdenum and the gold atoms display octahedral and linear geometries, respectively; the shortest intramolecular molybdenum-gold interaction is 4.52 Å. © 1995

Asymmetrical monocationic or neutral gold(II) complexes: X-ray crystal structure of [(C6F5)Au(CH2PPh2CH2)2AuPPh3]C1O4·0.5CH2Cl2

The reaction of [RAu(CH2PPh2CH2)2AuR] (R = C6F5 or 2,4,6-C6 F3H2) with Au(ONO2)PPh3, [Au(PPh3)2]ClO4 or [Au(PPh3)tht] ClO4 (tht = tetrahydrothiophene) leads to neutral [(C6F5)Au(CH2PPh2 CH2)2AuONO2] 1 or monocationic derivatives [RAu(CH2PPh2CH2) 2AuL]ClO4 [R = C6F5, L = PPh3(2) or tht(3); R = 2,4,6-C6 F3H2, L = PPh3(4) or tht(5)]. Complexes 3 and 5 react with anionic or neutral reagents, giving new neutral or monocationic gold(II) compounds. The structure of [(C6F5)Au(CH2PPh2CH2)2AuPPh3]ClO4 ·0.5CH2Cl2 (2) was determined by single-crystal X-ray diffraction. Crystals are triclinic, space group P, a = 12.468(2), b = 13.493(2), c = 18.283(3) Å, α = 108.13(1)°, β = 91.09(1)°, γ = 111.95(1)° and Z = 2. Final R is 0.0376 for 4906 unique observed reflections. The AuAu bond length is 2.6612(8) Å.We thank the Direction General de Investigacion Cientifica y Tecnica (no. PB88-0075).Peer reviewe

Synthesis of gold(III) complexes of 2-(diphenylthiophosphino)aniline

8 páginas, 2 figuras, 3 tablas, 1 esquema.The gold(III) complex [Au(C6F5)2(SPNH2)]CIO4 (1) containing the S,N-donor ligand 2-(diphenylthiop hosphino)aniline (S=PNH2) can be easily prepared by treatment of S=PNH2 with [Au(C6F5)2(OEt2)2]CIO4 and deprotonated with PPN(acac) to afford [Au(C6F5)2(SPNH)] (2). Complex 2 can also be obtained in a one-step reaction from SPNH2 and [Au(C6F5)2(acac)]. The electronic density in excess in 2 can be employed to incorporate a new metallic fragment to give the mixed complexes [Au(C6F5)2SPNH(MPPh3)]CIO4 (M=Au (3), Ag (4)). The crystal structures of 1 and 2 have been determined by X-ray diffraction, showing that the electronic density in excess in complex 2 is located in the Au-N-C fragment.The D.G>I.MEC/FEDER (CTQ2007-67273-C02-02) is thanked for financial support.Peer reviewe

Synthesis, coordination to Au(I) and photophysical properties of a novel polyfluorinated benzothiazolephosphine ligand

6 pages, 5 figures, 3 tables, 1 scheme.The reaction between Ph2PH and C6F5CNS leads to the formation of the polyfluorinated benzothiazolephosphine ligand Ph2P(CNS)(C6F4) 1. The mechanism of the reaction involves the addition of the phosphine to the isothiocyanate and subsequent intramolecular nucleophilic aromatic substitution. This new ligand reacts with gold(I) substrates producing complexes [AuCl{Ph2P(CNS)(C6F4)}] 2 and [Au(C6F5){Ph2P(CNS)(C6F4)}] 3. Both the ligand 1 and complexes 2 and 3 display phosphorescence with emissions arising from n(P) *(heterocyclic ring) excited state for 1 and *(heterocyclic ring) excited state for 2 and 3. DFT and TD-DFT calculations agree with these results.TheD.G.I.(MEC)/FEDER (CTQ2004-05495) project is acknowledged for financial support. M. Monge thanks the MECUniversidad de La Rioja for his research contract “Ramón y Cajal”.Peer reviewe

Combining Aurophilic Interactions and Halogen Bonding To Control the Luminescence from Bimetallic Gold−Silver Clusters

The luminescence in a series of new bimetallic gold−silver vapochromic structures can be efficiently switched among different colors simply by exposure to solvent vapors. The emission color in these systems is controlled by both aurophilic interactions and halogen bonding, which affect the emission energy through different orbitals.This work was supported by Project D.G- .I.(MEC)/FEDER (CTQ2007-67273-C02-02). T.L. thanks the M.I- .C.INN for a grant.Peer Reviewe