Hydrogen bonding to metals as a probe for an inverted ligand field.

Electron-rich, late transition metals are known to act as hydrogen-bonding (HBd) acceptors. In this regard, Pt(ii) centres in square-planar environments are particularly efficient. It is however puzzling that no convincing experimental evidence is currently available for the isoelectronic neighbour Au(iii) being involved in HBd interactions.

Platinum-mediated monohydration of SO.

The monohydration of SO2 has been achieved in solution mediated by a platinum-aquo complex. Benzamidate ligands play a key role along the process, acting as versatile proton shuttles. Finally, the platinum center allows the stabilization of benzimidic acid and a hydrogensulphite anion, the disfavored tautomers of benzamide and sulphonate, respectively.

An Organogold(III) Difluoride with a trans Arrangement.

The trans isomer of the organogold(III) difluoride complex [PPh ][(CF ) AuF ] has been obtained in a stereoselective way and in excellent yield by reaction of [PPh ][CF AuCF ] with XeF under mild conditions. The compound is both thermally stable and reactive. Thus, the fluoride ligands are stereospecifically replaced by any heavier halide or by cyanide, the cyanide affording [PPh ][trans-(CF ) Au(CN) ].

Gold(II) Trihalide Complexes from Organogold(III) Precursors.

The mononuclear gold(II) halide complexes [AuCl ] and [AuBr ] are formed in the gas phase by collision-induced homolytic splitting of the only Au-C bond in the monoalkylgold(III) precursors [CF AuX ] . The geometries of the whole series of [AuX ] complexes (X=F, Cl, Br, I) have been calculated by DFT methods. It has also been found that the neutral AuX molecules behave as unsaturated species, showing significant affinity for an additional X ligand.

(CF ) Au as a Highly Acidic Organogold(III) Fragment.

The Lewis acidity of perfluorinated trimethylgold (CF ) Au was assessed by theoretical and experimental methods. It was found that the (CF ) Au unit is much more acidic than its nonfluorinated analogue (CH ) Au, and probably sets the upper limit of the acidity scale for neutral organogold(III) species R Au. The significant acidity increase on fluorination is in line with the CF group being more electron-withdrawing than CH .

Anionic Derivatives of Perfluorinated Trimethylgold.

The homoleptic compound [PPh ][CF AuCF ] cleanly undergoes photoinduced oxidative addition of CF I to afford the organogold(III) derivative [PPh ][(CF ) AuI] in good yield and under mild conditions. This compound provides a convenient entry to the chemistry of the perfluorinated (CF ) Au fragment, the properties of which were analyzed with the aid of DFT methods and compared with those of the homologous non-fluorinated (CH ) Au moiety. It was found that reductive elimination of CX -CX in the former (X=F) requires a much higher energy barrier than in the latter (X=H) and is therefore considerably less favored.

Gold(I) Fluorohalides: Theory and Experiment.

The anionic trifluoromethylgold(I) derivatives [CF AuX] , which have been prepared and isolated as their [PPh ] salts in good yield, undergo thermally induced difluorocarbene extrusion in the gas phase, giving rise to the mixed gold(I) fluorohalide complexes [F-Au-X] (X=Cl, Br, I). These triatomic species have been detected by tandem mass spectrometry (MS2) experiments and their properties have been analyzed by DFT methods. The CF extrusion mechanism from the Au-CF moiety serves as a model for the CF insertion into the Au-F bond, since both reactivity channels are connected by the microreversibility principle.

Selective turn-off phosphorescent and colorimetric detection of mercury(II) in water by half-lantern platinum(II) complexes.

The platinum(ii) half-lantern dinuclear complexes [{Pt(bzq)(μ-C7H4NS2-κN,S)}2] () and [{Pt(bzq)(μ-C7H4NOS-κN,S)}2] () [bzq = benzo[h]quinolinate, C7H4NS2 = 2-mercaptobenzothiazolate, C7H4NOS = 2-mercaptobenzoxazolate] in solution of DMSO-H2O undergo a dramatic color change from yellowish-orange to purple and turn-off phosphorescence in the presence of a small amount of Hg(2+), being discernible by the naked-eye and by spectroscopic methods. Other metal ions as Ag(+), Li(+), Na(+), K(+), Ca(2+), Mg(2+), Ba(2+), Pb(2+), Cd(2+), Zn(2+) and Tl(+) were tested and, even in a big excess, showed no interference in the selective detection of Hg(2+) in water. Job's plot analysis indicated a 1 : 1 stoichiometry in the complexation mode of Hg(2+) by /.

Luminescent benzoquinolate-isocyanide platinum(II) complexes: effect of Pt⋅⋅⋅Pt and π⋅⋅⋅π interactions on their photophysical properties.

The neutral compounds [Pt(bzq)(CN)(CNR)] (R = tBu (1), Xyl (2), 2-Np (3); bzq = benzoquinolate, Xyl = 2,6-dimethylphenyl, 2-Np = 2-napthyl) were isolated as the pure isomers with a trans-C(bzq),CNR configuration, as confirmed by (13)C{(1)H} NMR spectroscopy in the isotopically marked [Pt(bzq)((13)CN)(CNR)] (R = tBu (1'), Xyl (2'), 2-Np (3')) derivatives (δ(13)C(CN) ≈ 110 ppm; (1) J(Pt,(13)C) ≈ 1425 Hz]. By contrast, complex [Pt(bzq)(C≡CPh)(CNXyl)] (4) with a trans-N(bzq),CNR configuration, has been selectively isolated from [Pt(bzq)Cl(CNXyl)] (trans-N(bzq),CNR) using Sonogashira conditions. X-ray diffraction studies reveal that while 1 adopts a columnar-stacked chain structure with Pt-Pt distances of 3.

Highly luminescent half-lantern cyclometalated platinum(II) complex: synthesis, structure, luminescence studies, and reactivity.

The half-lantern compound [{Pt(bzq)(μ-C(7)H(4)NS(2)-κN,S)}(2)]·Me(2)CO (1) was obtained by reaction of equimolar amounts of potassium 2-mercaptobenzothiazolate (KC(7)H(4)NS(2)) and [Pt(bzq)(NCMe)(2)]ClO(4). The Pt(II)···Pt(II) separation in the neutral complex [{Pt(bzq)(μ-C(7)H(4)NS(2)-κN,S)}(2)] is 2.910 (2) Å, this being among the shortest observed in half-lantern divalent platinum complexes.

Venous thromboembolism in COPD hospitalized patients.

Patients with chronic obstructive pulmonary disease (COPD) are at increased risk for venous thromboembolism (VTE). We analyzed a large Spanish database to determine the incidence of VTE in these patients during hospitalization. A retrospective chart review of cohort of consecutive patients admitted with COPD as the primary reason for discharge in Spain between January 1st 2006 and December 31st 2007 was performed.

Pt-Ag clusters and their neutral mononuclear Pt(II) starting complexes: structural and luminescence studies.

The mononuclear complexes [Pt(bzq)(S^S)] [S^S = pyrrolidinedithiocarbamate (pdtc 1), dimethyldithiocarbamate (dmdtc 2)] were prepared by reaction of [Pt(bzq)(NCMe)(2)]ClO(4) with an equimolecular amount of [NH(4)(pdtc)] and [Na(dmdtc)·2H(2)O] respectively in MeOH. Reactions of 1 and 2 with AgClO(4) in 1 : 1 and 2 : 1 molar ratios rendered the heteropolinuclear compounds [{Pt(bzq)(S^S)Ag}(2)](ClO(4))(2) (S^S = pdtc 3, dmdtc 4) and [{Pt(bzq)(S^S)}(2)Ag](ClO(4)) (S^S = pdtc 5, dmdtc 6) respectively. The X-ray studies on single crystals of 3 and 4 showed that both consist of tetranuclear [Pt(2)Ag(2)] clusters with the Pt-Ag and the Ag-Ag distances in the range of those corresponding to Pt-Ag dative bonds and argentophilic interactions.

Thirty-day mortality rate in women with cancer and venous thromboembolism. Findings from the RIETE Registry.

The influence of the site of cancer on outcome in cancer women with venous thromboembolism (VTE) is poorly understood. Reliable information on its influence might facilitate better use of prevention strategies. We assessed the 30-day outcome in all women with active cancer in the RIETE Registry, trying to identify if differences exist according to the tumor site.

Venous thromboembolism in acutely ill hospitalized medical patients.

Background: Acute and chronic illness, immobility, and procedural and pharmacologic interventions may predispose patients in the Internal Medicine Wards to venous thromboembolic disease (VTE). The purpose of this study was to determine the incidence of VTE in these patients.

Materials And Methods: A retrospective chart review of cohort of consecutive patients admitted to Internal Medicine wards in Spain between January 1st 2005 and December 31st 2007 was performed.

Synthesis of binuclear platinum complexes containing the ligands 8-naphthyridine, 2-aminopyridine, and 7-azaindolate. An experimental study of the steric hindrance of the bulky pentafluorophenyl ligands in the synthesis of binuclear complexes.

The bidentate N-donor ligands 2-aminopyridine (2-ampy), 7-azaindolate (aza) and 1,8-naphthyridine (napy) have been used to study the steric effect of pentafluorophenyl groups in the synthesis of binuclear platinum(II) complexes. The 2-ampy and aza ligands bridge two "Pt(C 6F 5) 2" fragments with Pt..

Synthesis and in solution and solid state structural study of intramolecular Pt...H interactions in pentafluorophenyl platinum(II) complexes containing the ligands triazene, formamidine, and 2-aminopyridine.

The preparation of the [NBu4][Pt(C6F5)3L] complexes (L=triazene, formamidine, 2-aminopyridine,) have been carried out. These ligands contain a hydrogen atom, with more or less acidic character, in a position suitable for establishing an intramolecular hydrogen bonding interaction with the metal center. This interaction has been detected in solution for; its 1H NMR spectrum shows that the resonance assignable to this hydrogen has platinum satellites.

Hydrogen-bond mediation of supramolecular aggregation in neutral bis-(C6F5)Pt complexes with aromatic H-bond donating ligands. A synthetic and structural study.

Six pentafluorophenylplatinum(II) complexes containing proton acceptor atoms (F) and pyridine-like aromatic ligands able to act as proton donors have been synthesized and characterized, with emphasis on the factors that mediate their supramolecular aggregation in the solid state--hydrogen bonds and pi-pi interactions. The crystal structure analyses of the mononuclear complexes cis-[Pt(C6F5)2(napy)](1), cis-[Pt(C6F5)2(CH2napy)](3), cis-[Pt(C6F5)2(2-ammpy)](5), and cis-[Pt(C6F5)2(2-bipym)](6) reveal the influence of D-HPt and D-HF (D=C, N) hydrogen bonding on the organization of molecules into stacks, which can be further interconnected to generate channels. The prevalence of hydrogen bonding over pi-pi interactions between aromatic rings in establishing the nature of the observed supramolecular aggregation is demonstrated.

Synthesis and Crystal and Electronic Structures of the Dinuclear Platinum Compounds [PEtPh(3)](2)[Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)] and [Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)]: A Computational Study by Density Functional Theory.

The electrolytic behavior of the dinuclear complexes [NBu(4)](2)[MM'(&mgr;-PPh(2))(2)(C(6)F(5))(4)] (M = M' = Pt (1), Pd (1a); M = Pt, M' = Pd (1b)) has been studied, showing electrochemically irreversible oxidation and related reduction processes. The chemical oxidation of the binuclear compound for M = M' = Pt, results in the formation of the binuclear Pt(III) compound [Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)]. The crystal structure analysis of both complexes has been carried out, showing very similar structures with similar Pt-C and Pt-P distances and analogous skeletons.

Synthesis and Reactivity of (Pentafluorophenyl)platinate(II) Complexes with Bridging 1,8-Naphthyridine (napy) and X Ligands (X = C(6)F(5), OH, Cl, Br, I, SPh). Crystal Structure of [NBu(4)][Pt(2)(&mgr;-napy)(&mgr;-OH)(C(6)F(5))(4)].CHCl(3).

By reaction of [NBu(4)](2)[Pt(2)(&mgr;-C(6)F(5))(2)(C(6)F(5))(4)] with 1,8-naphthyridine (napy), [NBu(4)][Pt(C(6)F(5))(3)(napy)] (1) is obtained. This compound reacts with cis-[Pt(C(6)F(5))(2)(THF)(2)] to give the dinuclear derivative [NBu(4)][Pt(2)(&mgr;-napy)(&mgr;-C(6)F(5))(C(6)F(5))(4)] (2). The reaction of several HX species with 2 results in the substitution of the bridging C(6)F(5) by other ligands (X) such as OH (3), Cl (4), Br (5), I (6), and SPh (7), maintaining in all cases the naphthyridine bridging ligand.

Syntheses and Structures of the Complexes cis-[M(C(6)F(5))(2)(N&arcraise;X)] (M = Pd, Pt; N&arcraise;X = 2-Iodoaniline, 2-Benzoylpyridine) Containing N&arcraise;X Acting as a Didentate Chelating Ligand and Displaying I-->M or O-->M Interactions.

Complexes cis-[M(C(6)F(5))(2)(THF)(2)] (M = Pd, Pt) are weak Lewis acids and react with the halocarbon ligand 2-iodoaniline (R-I) yielding the corresponding cis-[M(C(6)F(5))(2)(R-I)] [M = Pd (1), Pt (2)]. In these complexes a (C-)I-M bond is present. The use of other 2-haloanilines (halogen = F, Cl, Br) does not yield the analogous complexes because of the lesser nucleophilic character of the halogen involved.