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Characterisation
Kinds of Characterisation Terms modified by Characterisation Selected AbstractsIn vitro effects of lidocaine on the contractility of equine jejunal smooth muscle challenged by ischaemia-reperfusion injuryEQUINE VETERINARY JOURNAL, Issue 1 2010M. GUSCHLBAUER Summary Reasons for performing study: Post operative ileus (POI) in horses is a severe complication after colic surgery. A commonly used prokinetic drug is lidocaine, which has been shown to have stimulatory effects on intestinal motility. The cellular mechanisms through which lidocaine affects smooth muscle activity are not yet known. Objectives: To examine the effects of lidocaine on smooth muscle in vitro and identify mechanisms by which it may affect the contractility of intestinal smooth muscle. Hypothesis: Ischaemia and reperfusion associated with intestinal strangulation can cause smooth muscle injury. Consequently, muscle cell functionality and contractile performance is decreased. Lidocaine can improve basic cell functions and thereby muscle cell contractility especially in ischaemia-reperfusion-challenged smooth muscle. Methods: To examine the effects of lidocaine on smooth muscle function directly, isometric force performance was measured in vitro in noninjured and in vivo ischaemia-reperfusion injured smooth muscle tissues. Dose-dependent response of lidocaine was measured in both samples. To assess membrane permeability as a marker of basic cell function, release of creatine kinase (CK) was measured by in vitro incubations. Results: Lidocaine-stimulated contractility of ischaemia-reperfusion injured smooth muscle was more pronounced than that of noninjured smooth muscle. A 3-phasic dose-dependency was observed with an initial recovery of contractility especially in ischaemia-reperfusion injured smooth muscle followed by a plateau phase where contractility was maintained over a broad concentration range. CK release was decreased by lidocaine. Conclusion: Lidocaine may improve smooth muscle contractility and basic cell function by cellular repair mechanisms which are still unknown. Improving contractility of smooth muscle after ischaemia-reperfusion injury is essential in recovery of propulsive intestinal motility. Potential relevance: Characterisation of the cellular mechanisms of effects of lidocaine, especially on ischaemia-reperfusion injured smooth muscle, may lead to improved treatment strategies for horses with POI. [source] Synthesis and Characterisation of a New Cu(O2CNAllyl2)2 Carbamato Complex and an Unusual Polymeric CuI Complex [CuI4Cl4(NHAllyl2)4]n: New Insights into Metal Carbamato ChemistryEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 35 2009Alberto Albinati Abstract Transition-metal N,N -dialkylcarbamato complexes represent an interesting class of compounds that can be conveniently used as precursors for the controlled formation of inorganic compounds, typically oxides. They can also be used as convenient precursors for chemical grafting of metal oxides on oxide surfaces as well as for the synthesis of inorganic,organic hybrid materials. In this last case, the presence of double bonds on the complex would enable its covalent embedding into a polymer matrix through reaction with suitable monomers. To this aim, we addressed the synthesis of an allyl-functionalised copper carbamato complex. During the synthesis of the N,N -diallylcarbamato complex Cu(O2CNAllyl2)2 (Cu1), the formation of the crystalline and unusual polymeric CuI complex [CuI4Cl4(NHAllyl2)4]n (Cu2) was observed. The new compound was characterised by X-ray single crystal diffraction and FTIR, 1H and 13C NMR spectroscopic analysis. In an attempt to investigate the redox mechanism and the equilibria leading to the formation of the observed unusual CuI polymeric complex, gas chromatography coupled with mass spectrometry (GC,MS) experiments were carried out, which allowed us to identify 3,4-dimethylpyrrole as the oxidation product of the reaction, leading to the reduction of CuII to CuI.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Synthesis and Characterisation of [XeF5]3[Ti4F19] Containing a Discrete [Ti4F19]3, AnionEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 29-30 2009Zoran Mazej Abstract The complex [XeF5]3[Ti4F19] was prepared by reaction of XeF2, TiF4 and UV-irradiated elemental fluorine in anhydrous hydrogen fluoride as the solvent. The crystal structure of [XeF5]3[Ti4F19] consists of [XeF5]+ cations and discrete [Ti4F19]3, anions. The [XeF5] units have usual slightly distorted pseudo-octahedral symmetry. Contrary to the previously reported [Ti4F18]2, anion, where each TiF6 octahedron shares three apexes with three other octahedra, in [Ti4F19]3,, only two ,3 -[TiF6] octahedra share three apexes with three other [TiF6] units. Each of the remaining two ,2 -[TiF6] octahedra shares only two vertices with two of the above-mentioned ,3 -[TiF6] moieties. The Raman spectrum of [XeF5]3[Ti4F19] is in agreement with the presence of [XeF5]+ cations and [Ti4F19]3, anions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Synthesis and Characterisation of (Alkoxybenzimidazolin-2-ylidene)palladium Complexes: The Effect of Ancillary Ligands on the Behaviour of PrecatalystsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2009Murray V. Baker Abstract A series of new N-heterocyclic carbene (NHC),palladium(II) complexes bearing electron-rich benzimidazolin-2-ylidene ligands are described and structurally and spectroscopically characterised. These (benzimidazolin-2-ylidene)palladium complexes bear butoxy groups to increase the solubility and perhaps influence the catalytic activity by increasing the electron density around the metal centre. The effect of varying the ancillary ligands is investigated, although these ligands do not appear to significantly alter the activity of the complexes as precatalysts. Preliminary studies indicate the complexes act as precatalysts with moderate activity in the Mizoroki,Heck and Suzuki,Miyaura coupling reactions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Synthesis, Characterisation and Optical Properties of Silica Nanoparticles Coated with Anthracene Fluorophore and Thiourea Hydrogen-Bonding SubunitsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 36 2008Pilar Calero Abstract Bifunctionalised hybrid silica nanoparticles have been synthesised and characterised, and their optical emission properties in the presence of certain anions in acetonitrile solutions have been studied. The alkoxysilane derivatives N -butyl- N, -[3-(trimethoxysilyl)propyl]thiourea (1), N -phenyl- N, -[3-(trimethoxysilyl)propyl]thiourea (2) and 3-[(anthracen-10-yl)methylthio]propyltriethoxysilane (3) were prepared and used to functionalise uncoated LUDOX silica nanoparticles with a mean diameter of 18,±,2 nm. The functionalisation of the nanoparticle surfaces was carried out by two different approaches. The first approach relies on the consecutive grafting of the two subunits. In this protocol, the nanoparticles were first functionalised with anthracene derivative 3 (solid NA), and then treated with the corresponding binding sites 1 or 2 to result in the NA-Pt3 and NA-Bt3 solids. The second approach deals with the simultaneous grafting of 1 or 2 and the signalling subunit 3 in different ratios. This method was used for the preparation of the NA1Pt1, NA1Bt1, NA1Pt3 and NA1Bt3 nanoparticles. The bifunctionalised silica nanoparticles were characterised by using standard techniques. Acetonitrile suspensions of NA nanoparticles (5 mg in 20 mL) showed anthracene bands centred at ca. 350, 370 and 390 nm. Upon excitation at 365 nm, a typical emission band with fine structure in the 390,450 nm range was observed. Similar absorption and emission spectra were found for the bifunctionalised nanoparticles. The work is completed with a prospective study of the fluorescence of the prepared nanoparticles in the presence of organic (acetate, benzoate) and inorganic (F,, Cl,, Br,, CN,, HSO4, and H2PO4,) anions. The apparent binding constants (adsorption constants) for the interaction of NA-Pt3 with anions in acetonitrile were determined by performing a Langmuir-type analysis of fluorescence titration data.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Aluminium Complexes of a Phenoxyimine Ligand with a Pendant Imidazolium Moiety: Synthesis, Characterisation and Evidence for Hydrogen Bonding in SolutionEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 35 2008Stefano Milione Abstract Novel alkylaluminium complexes (phim)AlMe2 (1) and(phimid)AlR2+Br, [R = Me (2), R = iBu (3)] bearing the Schiff base ligands 3,5- tBu2 -2-(OH)C6H2CH=NiPr (phim -H) and3,5- tBu2 -2-(OH)C6H2CH=NCH2CH2[CH(NCHCHNiPr)]Br(phimid -H·Br) have been prepared and fully characterised. Complexes 1,3 each have a tetrahedral structure, with the aluminium atom surrounded by the oxygen and nitrogen atoms of the chelating ligand and two alkyl groups. The structures of phimid -H·Br and of complex 1 have been determined by X-ray diffraction studies. Investigation of the solution structures of 1,3 by 1H NMR spectroscopy revealed that the coordinated phimid ligand is involved in hydrogen bonding with bromide anion. Treatment of 1 with B(C6F5)3 led smoothly to (phim)Al(C6F5)Me (4) by transfer of a C6F5 group from MeB(C6F5)3, to the initially formed coordinatively unsaturated cationic intermediate. In contrast, treatment of 2 with one equiv. of B(C6F5)3 afforded the cationic monomethyl species (phimid)AlMeBr+,MeB(C6F5)3, (5), stabilised by the coordination of the bromide anion acting as a Lewis base.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Monocyclopentadienyl Phenoxido,Amino and Phenoxido,Amido Titanium Complexes: Synthesis, Characterisation, and Reactivity of Asymmetric Metal Centre DerivativesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 29 2008Giuseppe Alesso Abstract Reduction of phenol,imine derivatives R,N=CH(3,5-R2C6H2 -2-OH) (R = tBu; R, = C6H51a, p -MeC6H41b, Cy 1c, tBu 1d, 2,6-Me2C6H31e; R = H; R, = p -MeC6H41f; Cy = cyclohexyl) with MBH4 (M = Li, Na) or AlLiH4 in ethyl ether or thf at room temperature affords the phenol,amine compounds R,NHCH2(3,5-R2C6H2 -2-OH) 2a,c and 2e,f. The N -R-[2,4-di- tert -butyl]benzo-1-oxa-3-azine species (R = tBu 2d1, 2,6-Me2C6H32e1) are obtained by Mannich reaction of 2,4-di- tert -butylphenol with RNH2 in refluxing methanol. Intermediate 2d1 is converted in ethanol at room temperature into N - tert -butyl[2-hydroxy-3,5-di- tert -butyl]benzylamine (2d), whereas 2e is not obtained from 2e1 by using this procedure.N -alkyl,N - tert -butyl[2-hydroxy-3,5-di- tert -butyl]benzylaminecompounds tBuN(R)CH2(3,5- tBu2C6H2 -2-OH) (R = Me 2g, Et 2h, nPr 2i, CH2Ph 2j) are also prepared by the appropriate synthetic method. Treatment of 2a,c with 1 equiv. of TiCpCl3 in the presence of 2.5 equiv. of NEt3 in hexane at room temperature gives the monocyclopentadienyl phenoxido,amido monochloride complexes TiCp[R,NCH2(3,5- tBu2C6H2 -2-O)]Cl (R, = C6H53a, R, = p -MeC6H43b, R, = Cy 3c). The analogous complex Ti(,5 -C5H4SiMe2Cl)[C6H5NCH2(3,5- tBu2C6H2 -2-O)]Cl (4a) results from the reaction of 2a with Ti(,5 -C5H4SiMe2Cl)Cl3. Nevertheless, 2d reacts with TiCpCl3 in hexane in the presence of NEt3 at room temperature yielding the monocyclopentadienyl phenoxido dichloride compound TiCp[tBuNHCH2(3,5- tBu2C6H2 -2-O)]Cl2 (5), whereas in ethyl ether and in the absence of NEt3 adduct 5·HCl is obtained, which is further converted into TiCp[tBuNCH2(3,5- tBu2C6H2 -2-O)]Cl (3d) by addition of a NEt3/ethyl ether solution. The reaction of TiCpCl3 with 2a in the presence of 2.5 equiv. of NEt3 in a polar solvent (thf, CH2Cl2 or toluene) at room temperature affords TiCp[Ph(H)NCH2(3,5- tBu2C6H2 -2-O)]Cl (6a) as a mixture of two stereoisomers. All the reported compounds were characterised by the usual analytical and spectroscopic methods and the molecular structures of 2a, 2d, 2e and 3d were determined by X-ray diffraction analysis from suitable single crystals. Preliminary studies of catalytic activity for ethylene polymerisation by using solid methylaluminoxane as cocatalyst were performed.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Expanding the Range of "Daniphos"-Type P,P- and P,N-Ligands: Synthesis and Structural Characterisation of New [(,6 -arene)Cr(CO)3] ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 31 2007Elisabetta Alberico Abstract New P,P- and P,N-ligands have been synthesised whose core structure is an [(,6 -arene)Cr(CO)3] unit. These new ligands, which extend the range of "Daniphos" ligands, are endowed with central and planar chirality and have been prepared through a stereoselective synthetic strategy from optically pure benzylamines bearing a second substituent on the arene other than the benzyldimethylamino group. Because the two faces of unsymmetrically 1,2- and 1,3-disubstituted benzylamine are diastereotopic, which means that diastereomeric complexes arise upon coordination of theCr(CO)3 fragment to either of these two faces, the synthetic plan has been adjusted by exploiting the trimethylsilyl group as a temporary steric modulator in order to access both complexes with high diastereoselectivity. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Synthesis and Characterisation of Semi-Bridging Molybdenum Borylene ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 27 2007Holger Braunschweig Abstract Investigation of the reactivity of the molybdenum borylene complex [(OC)5Mo=B=N(SiMe3)2] towards the late transition metal complexes [M(PCy3)2] (M = Pd, Pt) indicated the formation of [(OC)4Mo(, - CO){, - BN(SiMe3)2}Pd(PCy3)] and [(Cy3P)(OC)3Mo(, - CO){, - BN(SiMe3)2}Pt(PCy3)], respectively, as the first Mo-based semi-bridging borylene complexes. The new complexes were fully characterised spectroscopically and analysed by X-ray diffraction. The conclusions drawn from the experimental data for the ligand-metal interactions for this particular coordination mode of a borylene group were supported by DFT computations.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Synthesis and Crystallographic Characterisation of the Heterodimetallic Complex [(Dibenzo-18-crown-6)K(,-Cl)3Ru(,6 - p -cymene)]EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 21 2007Carsten A. Vock Abstract The triple-chlorido-bridged heterodimetallic dinuclear complex [(dibenzo-18-crown-6)K(,-Cl)3Ru(,6 - p -cymene)] containing an (,6 -arene)RuII fragment and a Group 1 metal crown ether fragment was synthesized and characterized by spectroscopy and X-ray crystallography. The solid-state structure clearly reveals the presence of the triple-chlorido-bridged dinuclear complex, whereas NMR investigations in different deuteriated solvents reveal the presence of an essentially 1:1 mixture of 1 and starting materials, indicating the presence of a dynamic equilibrium. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Synthesis and Structural Characterisation of Copper(II) 15-Metallacrown-5 Complexes with PbII, HgII, AgI, NaI and YIII Central Metal IonsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2007Sabry Hamed Seda Abstract The new copper(II) 15-metallacrown-5 complexes with the central metal ions PbII, HgII, AgI, NaI and YIII, with the formula [MCu5L5]Xn {H2L is 2-picolinehydroxamic acid or (S)-phenylalaninehydroxamic acid and X, is NO3, or Cl,}, have been synthesised and characterised by NMR and UV/Vis spectroscopy, electrospray mass spectrometry and elemental analysis. The PbII - and HgII 15-metallacrown-5 complexes were obtained in the crystalline form as pyridine adducts [PbCu5(picha)5(py)6](NO3)2·3(py) and [HgCu5(picha)5(py)7](NO3)2·2(py) and their X-ray crystal structures were determined. In both complexes, each peripheral CuII ion of the metallacrown is coordinated by one pyridine molecule bonded in the axial position. In the case of the PbII derivative, one additional axial pyridine molecule is bound to the central metal ion, while in the case of the HgII derivative, two axial pyridine ligands are bound to the central HgII ion. The relative stability of the copper(II) 15-metallacrown-5 complexes with various central metal ions was determined on the basis of competition reactions. The relative preference of the 15-metallacrown-5 system for the central metal ion follows the series NaI, AgI < lanthanide(III), HgII < PbII.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Cobalt and Nickel Complexes Bearing Pyrazolyliminophosphorane Ligands: Synthesis, Characterisation and Catalytic Ethylene Oligomerisation BehaviourEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2006Cheng Zhang Abstract Treatment of 1-(2,-azidophenyl)-3,5-dimethylpyrazole (1) with Ph2PR (R = Ph, Me) and (Ph2P)2CH2, respectively, affords the pyrazolyliminophosphoranes 2, 3 and 4. Reaction of 2 or 3 with [NiCl2(dme)] or NiBr2 yields the N,N-chelate nickel complexes 5,8, and with CoCl2 complexes 9 and 10. Reaction of 4 with [NiCl2(dme)], NiBr2 and CoCl2, respectively, affords the N,N,P-chelate complexes 11,13. Compounds 2,4 were characterised by 1H, 13C, 31P NMR and IR spectroscopy and elemental analysis, while complexes 5,13 were characterised by IR spectroscopy and elemental analysis. The structures of complexes 5, 9 and 12 were further characterised by single-crystal X-ray diffraction techniques. Complexes 5,13 are active catalysts for ethylene oligomerisation upon activation with alkylaluminium derivatives(Et2AlCl, MAO or MMAO). These complexes exhibit good to high catalytic activities (up to 3.54,×,106 g,mol,1,h,atm for the nickel complexes and 5.48,×,105 g,mol,1,h,atm for the cobalt complexes). The effects of varying ethylene pressure, temperature and aluminium co-catalyst/Ni or Co ratios with complexes 5, 9, 11 and 12 are reported. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Cationic Brųnsted Acids for the Preparation of SnIV Salts: Synthesis and Characterisation of [Ph3Sn(OEt2)][H2N{B(C6F5)3}2],[Sn(NMe2)3(HNMe2)2][B(C6F5)4] and [Me3Sn(HNMe2)2][B(C6F5)4]EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 16 2006Yann Sarazin Abstract Ph3SnN(SiMe3)2 (1) was prepared in good yields by reaction of [{NaN(SiMe3)2}2·THF] (2) with Ph3SnF. Treatment of 1 with [H(OEt2)2][H2N{B(C6F5)3}2] (4) in dichloromethane afforded the stannylium cation [Ph3Sn(OEt2)][H2N{B(C6F5)3}2] (5), which was characterised by 1H, 13C{1H}, 11B, 19F and 119Sn NMR spectroscopy. The reaction of Sn(NMe2)4 with [Ph2MeNH][B(C6F5)4] (3) gave the amidotin(IV) compound [Sn(NMe2)3(HNMe2)2][B(C6F5)4] (6) which proved very stable towards ligand substitution and resisted treatment with Et2O, THF, TMEDA and pyrazine. Two new Brųnsted acid salts [H(NMe2H)2][B(C6F5)4] (7) and [(C4H4N2)H·OEt2][H2N{B(C6F5)3}2] (8) were synthesised. The reaction of 7 with Sn(NMe2)4 in Et2O allowed the preparation of 6 in a much improved yield (83,%). The treatment of 7 with Me3SnN(SiMe3)2 in Et2O yielded [Me3Sn(HNMe2)2][B(C6F5)4] (9) nearly quantitatively. Compounds 1, 2, 6, 8 and 9 were characterised by single-crystal X-ray diffraction analyses; 6 is the first example of a structurally characterised amidotin(IV)cation.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Synthesis and Structural Characterisation of Palladium and Group-12 Metal Complexes with a Hybrid Phosphanylphosphonate Ferrocene LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 5 2006Abstract Diethyl [1,-(diphenylphosphanyl)ferrocenyl]phosphonate (1) was synthesised by stepwise metallation/functionalisation of 1,1,-dibromoferrocene and studied as a ligand for palladium(II) and group-12 metals. Treatment of [PdCl2(cod)] (cod = ,2:,2 -cycloocta-1,5-diene) with 1 in 1:1 or 1:2 molar ratios gave, respectively, the dinuclear, chloride-bridged complex [{Pd(,-Cl)Cl(1 -,P2)}2] (2) and the mononuclear complex trans -[PdCl2(1 -,P2)2] (3), where 1 coordinates exclusively through the phosphane function. The reactions between 1 and group-12 metal bromides MBr2 in a 1:1 molar ratio gave the adducts [MBr2(1)] [M = Zn (4), Cd (5), and Hg (6)], whose crystal structures change considerably with the metal ion. Thus, whereas 4 is a molecular complex with 1 coordinating as an O1,P2 -chelate, its cadmium(II) analogue is a polymer built up from symmetric {CdBr(,-Br)}2 units interconnected by pairs of O1,P2 -bridging phosphanylphosphonate ligands. Finally, the mercury(II) complex 6 is a halide-bridged dimer, [{Hg(,-Br)Br(1 -,P2)}2]. However, this compound is structurally fluxional in solution (NMR spectra) and, in the crystal, it attains a structure similar to 5 owing to weak interactions between mercury and phosphonate-O1 atoms from adjacent molecules. An isomer to 6, [{HgBr2(1 -,2O1,P2)}2] (7), was isolated from attempted alkylation of 6 and structurally characterised as a dimer, where ligands 1 bridge two {HgBr2} units. All compounds were studied by spectroscopic methods (IR, NMR, mass) and the solid-state structures of 1, 2·,H2O, 3·4,CHCl3, 4, 5, 6·5,C6H6, and 7 have been determined by single-crystal X-ray diffraction. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Synthesis, Structural Characterisation and Reactions of Some Vinylgold(I) Phosphane ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2006Fabian Mohr Abstract A series of vinylgold(I) complexes [Au(CR=CHR)L] (R = H, Me; L = PPh3, PPh2Me, PPhMe2) were prepared from the reaction of the Grignard reagents [MgBr(CR=CHR)] (R = H, Me) with the gold(I) phosphane complexes [AuCl(L)] (L = PPh3, PPh2Me, PPhMe2) at low temperature. The complexes were characterised by various spectroscopic techniques and, in the case of [Au(CMe=CHMe)(PPh3)], by a single-crystal X-ray structure determination. The gold,carbon bonds of these vinylgold(I) complexes are easily cleaved by acids and, in the presence of potassium permanganate, by species containing acidic protons. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] The Synthesis and Characterisation of Bis(phosphane)-Linked (6 - p -Cymene)ruthenium(II),Borane CompoundsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2005Adrian B. Chaplin Abstract The reaction of [(,6 - p -cymene)RuCl2]2 with some bis(phosphane) ligands (dppm, dppe, dppv, dppa, dpp14b, dppf) has been investigated. In general mixtures of products were obtained, although the pendant phosphane complexes [(,6 - p -cymene)RuCl2(,1 -dppv)] and [(,6 - p -cymene)RuCl2(,1 -dppa)] were isolated and characterized in the solid state by X-ray diffraction. The later complex was obtained in lower yield and undergoes an equilibration reaction resulting in the formation of a dimeric species, where the dppa bridges two ruthenium centres, and uncoordinated phosphane; the bridging species was also structurally characterised in the solid state. In contrast, the reaction of [(,6 - p -cymene)RuCl2(PPh3)] with dppa in the presence of [NH4]PF6 results in the formation of [(,6 - p -cymene)RuCl(PPh3)(,1 -dppa)]PF6, which is stable in solution. A series of linked ruthenium,borane complexes, viz. [(,6 - p -cymene)RuCl2(,1 -phosphane-BH3)] (phosphane = dppm, dppe, dppv, dppa, dpp14b, dppf) and [(,6 - p -cymene)RuCl(PPh3)(,1 -dppa-BH3)]PF6 have been prepared from isolated pendant phosphane complexes, those generated in situ, or from a preformed phosphane,borane adduct. The solid-state structures of [(,6 - p -cymene)RuCl2(,1 -dppm-BH3)], [(,6 - p -cymene)RuCl2(,1 -dppe-BH3)] and [(,6 - p -cymene)RuCl2(,1 -dppv-BH3)] have been determined by X-ray diffraction analysis. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Current-Voltage Characterisation of Monolayer-Supported Au-Nanoclusters by Scanning Tunnelling Microscopy under Ambient ConditionsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 18 2005Volker Jacobsen Abstract The current-voltage characteristics of a double-tunnel junction based on a gold crystallite with a diameter of ca. 2 nm, separated from a gold surface by ca. 1 nm was investigated by scanning tunnelling microscopy. The sample architecture was built by attaching gold nanoparticles covered with 2-mercaptosuccinic acid to an atomically flat gold surface which was covered by a self-assembled monolayer (SAM) of 6-amino-1-hexanethiol. Surface plasmon and infrared spectroscopy as well as STM imaging were employed to identify suitable preparation conditions and prove the existence of the desired architecture. No reproducible steps in the current-voltage characteristics are observed on this system under ambient conditions. Nonetheless, a sound signature for tunnelling through the double-tunnel junction is established by a quantitative fit of the averaged experimental data to a theoretical model of a single-tunnel junction. Firstly, the current on the particle is strongly reduced at low absolute external voltage and secondly the current voltage characteristics are asymmetric. Since both deviations from theory are absent in reference experiments on the bare monolayer, they may serve as a robust signature for double-tunnel junctions and open the door to the investigation of single-electron tunnelling under ambient conditions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Synthesis, Crystal Structure and Characterisation of a Novel Chiral Mixed-Valence Vanadium Oxide Hybrid, [V5O11(dien)3]EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2005Ming-Lai Fu Abstract The novel chiral mixed-valence vanadium oxide hybrid [V5O11(dien)3] (1) (dien = NH2C2H4NHC2H4NH2) has been synthesised by a hydrothermal reaction of V2O5 and dien in aqueous solution and characterised by elemental analysis, IR spectroscopy, TG-DSC analysis, magnetism, EPR spectroscopy, single-crystal X-ray diffraction and powder XRD. The X-ray diffraction analysis revealed that the structure of 1 can be regarded as being constructed from two [VVO4]3, groups bicapping three [VIVO(dien)]2+ units to form a discrete asymmetric pentanuclear vanadium complex with the dien ligands coordinating directly to the vanadium(IV) centres. Compound 1 exhibits an interesting tube-like 3D supramolecular structure due to abundant hydrogen-bonding interactions between the oxygen atoms of the inorganic backbone and the hydrogen atoms of the dien ligands from adjacent molecules. The variable-temperature magnetic susceptibility data of 1 suggest a weak ferromagnetic interaction among V4+ ions in the cluster. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Cationic Iridium Complexes with Chiral Dithioether Ligands: Synthesis, Characterisation and Reactivity under Hydrogenation ConditionsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2005Leticia Flores-Santos Abstract A series of cationic IrI complexes containing chiral dithioether ligands have been prepared in order to study the influence of the sulfur substituents and the metallacycle size on the acetamidoacrylate hydrogenation reaction. In the case of complexes 6, 7 and 10, a mixture of diastereomers is observed in solution due to the sulfur inversion processes. In contrast, this fluxional behaviour is efficiently controlled by using bicyclic ligands which inhibit the S-inversion in complexes 8 and 9. The solid-state structure of complex 10b shows only one diastereomer with the sulfur substituents in a relative anti disposition and in an overall configuration of SCSCSSSS at the coordinated dithioether ligand. Iridium complexes containing seven- and six-membered metallacycles (6b,d, 7b,c, 10a,b) react with the substrate through S-ligand substitution, and the rate of this substitution is related to the position of the fluorine atom on the aromatic ring. On the contrary, complexes containing a bismetallacycle (8 and 9) are not displaced by the substrate. The catalytic hydrogenation activity of complexes 8 and 9 is analysed in terms of the high stability of the corresponding dihydride complexes (13 and 14). In both cases, only two of the four possible diastereomeric dihydride species are formed in solution. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Synthesis and Characterisation of New Iridium Complexes with the (4S)-2-[2-(Diphenylphosphanyl)phenyl]-4-isopropyl-1,3-oxazoline Ligand That Catalyse Asymmetric Michael ReactionsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 9 2005Daniel Carmona Abstract The chiral iridium compounds [IrCl(COE){(S)-PN}] {COE = cyclooctene, PN = (4S)-2-[2-(diphenylphosphanyl)phenyl]-4-isopropyl-1,3-oxazoline, (1)}, [Ir(acac)ClH{(S)-PN}] {Hacac = acetylacetone, (2)} and [Ir{(S)-PN}2]A {A = Cl (3a,b); BF4 (4a,b); PF6 (5a,b)} have been prepared, characterised and employed as catalysts for the asymmetric Michael addition of keto or cyano esters to ,,,-unsaturated carbonyl compounds. The X-ray molecular structures of compounds 2 and 5b are reported. The model catalytic intermediates [IrH(NCCHCO2R){(S)-PN}2]Cl {R = Me (12), Et (13)} have also been isolated and characterised. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Synthesis and Characterisation of Novel Complexes Containing Group 15 Elements and Their Potential Use as Molecular Precursors for the Formation of Transition Metal PnictidesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2005Manfred Scheer Abstract The reaction of [{W(CO)5}2PCl] with K[Co(CO)4] yields the novel compounds [{W(CO)4Co2(CO)6}{µ3 -PW(CO)5}2] (3) and [{(CO)4WCo3(CO)6}{µ3 -PW(CO)5}3] (4) along with known derivatives [Co2(CO)6{,,,2 -PW(CO)5}2] (1) and [Co3(CO)9{,3 -PW(CO)5}] (2). The complex [{W2(CO)8(,-CO)}{,,,2:,1:,1 -PW(CO)5}2)] (5) was synthesised by treating Na2[W2(CO)10] with PBr3. Reaction of K[Mn(CO)5] with SbCl3 affords [Sb{Mn(CO)5}3] (6) in high yields. The spectroscopic and structural characterisation of the novel products is discussed, as well as the thermolytic behaviour of 2, 3 and 6 for the potential formation of novel phases of transition metal pnictides. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] endo and exo Coordination of Indanol: Synthesis, Isolation and Structural Characterisation of [H3Ru3(endo -Indanol)(C6Me6)2(O)]+ and [H3Ru3(exo -Indanol)(C6Me6)2(O)]+ as Their Tetrafluoroborate SaltsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2004Ludovic Vieille-Petit Abstract The reaction of 2,3,4,7-tetrahydro-1H -inden-2-ol with ruthenium chloride hydrate in refluxing ethanol yields the chloro-bridged dinuclear complex [RuCl2(indanol)]2 (1). The mononuclear complex [Ru(indanol)(H2O)3]2+ (2), formed in situ from 1 in aqueous solution, reacts with the dinuclear complex [H3Ru2(C6Me6)2]+ to give a trinuclear arene-ruthenium cluster as a mixture of two isomers, the cations [H3Ru3(endo -indanol)(C6Me6)2(O)]+ (3a) and [H3Ru3(exo -indanol)(C6Me6)2(O)]+ (3b), in a 1:1 ratio. The hydroxy function of the indanol ligand is oriented towards the ,3 -oxo cap of 3a, whereas the OH group is bent away from the metal skeleton of 3b. These two isomers, which can easily be separated by silica-gel chromatography, were isolated and characterised as their tetrafluoroborate salts. The single-crystal X-ray structure analysis of [3a][BF4] shows a strong intramolecular hydrogen bond between the ,3 -oxo ligand and the hydroxyl function, which even persists in acetone solution, as demonstrated by NMR spectroscopy. On the other hand, the hydroxy function of 3b was found to be free in the solid state as well as in solution, as shown by an X-ray crystal structure analysis and by NMR spectroscopy. The catalytic activities of the water-soluble trinuclear cations 3a and 3b for the hydrogenation of benzene to give cyclohexane under biphasic conditions are considerably different, the exo isomer 3b being more active than the endo isomer 3a. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Synthesis and Characterisation of Coordination Polymers of CuII and ZnII with 1,3-Bis(1,2,3,4-tetrazol-2-yl)propane , Rotational Freedom of the Donor Group Favours Structural DiversificationEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 18 2004Robert Bronisz Abstract The novel bidentate ligand 1,3-bis(1,2,3,4-tetrazol-2-yl)propane (pbtz), which possesses a flexible spacer, was synthesised in order to investigate the influence of the flexibility of ligand molecules on the architecture of coordination polymers. For that purpose the reactions between pbtz and M(ClO4)2·6H2O salts (M = CuII and ZnII) were performed. The complexes [{Cu(pbtz)3}(ClO4)2], and [{Zn(pbtz)3}(ClO4)2·2EtOH], were characterised by IR and UV/Vis spectroscopy and their crystal structures were determined by single-crystal X-ray diffraction measurements. In both compounds the pbtz ligand molecules act as N4,N4, connectors bridging the central atoms, and the 2-substituted tetrazole rings coordinate in a monodentate fashion to the central atoms forming M(tetrazole)6 cores. [{Cu(pbtz)3}(ClO4)2], was isolated as a 1D coordination polymer. The copper(II) ions are triply bridged by ligand molecules, leading to the formation of infinite 1D chains. A highly unusual manner of bridging, with the tethering of two neighbouring central atoms by the same kind of ligand molecules, although possessing different conformations, is observed. In [{Zn(pbtz)3}(ClO4)2·2EtOH], the six-coordinate zinc(II) ions, which are bridged by single ligand molecules, serve as topological nodes, leading to the formation of a 3D ,-polonium-type network. The crystal structure of the ZnII complex contains only one such net solvated by ethanol molecules. A conformational analysis of the ligand molecules in both compounds demonstrates that the flexibility of the pbtz and the ability of the tetrazole rings in particular to adopt various, relative orientations is responsible for the diversity of the architectures of the obtained complexes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Synthesis and Characterisation of Ternary Cage Compounds with Adamantane-Like M4P4Si2 (M = Al, Ga, In) Core StructuresEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 16 2003Carsten von Hänisch Abstract The reactions of [LiAl(PH2)4] or [NaAl(PH2)4] with Et2SiCl2 or iPr2SiCl2 yield the dialkyldiphosphanylsilanes Et2Si(PH2)2 (1) and iPr2Si(PH2)2 (2), respectively. Both compounds were identified by NMR spectroscopy as well as mass spectrometry. Compound 2 reacts with MEt3 (M = Al, Ga, In) to form the cage compounds [iPr2Si{P(H)MEt2}2]2 (3: M = Al, 4: M = Ga, 5: M = In). These three clusters were fully characterised by NMR and IR spectroscopy as well as by single-crystal X-ray diffraction. The central structural motif of 3,5 is an adamantane-like cage composed of four metal, four phosphorus and two silicon atoms. They are the first ternary clusters with these combinations of elements and crystallise isotypical in the triclinic space group P ; the lattice constants are: 3: a = 1129.0(6), b = 1164.8(8), c = 1750.6(8) pm; , = 83.63(5), , = 81.53(4), , = 73.39(5)°; 4: a = 1125.9(7), b = 1159.0(7), c = 1744.7(7) pm; , = 83.71(4), , = 81.89(4), , = 73.05(5)°; 5: a = 1147.4(2), b = 1174.7(2), c = 1753.3(4) pm; , = 85.32(3), , = 82.03(3), , = 73.40(3)°. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Synthesis and Microstructural Characterisation of Two New One-Dimensional Members of the (A3NiMnO6),(A3Mn3O9), Homologous Series (A = Ba, Sr)EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2003Marķa Hernando Abstract Two new members of the one-dimensional (A3NiMnO6),(A3Mn3O9), homologous series, with the compositions (Sr0.75Ba0.25)5NiMn3O12 and Sr9Ni2Mn5O21, have been synthesised. Their structures can each be described as a hexagonal array of infinite one-dimensional chains of face-sharing polyhedra, running parallel to the c axis and separated by the Sr/Ba cations. The structure of (Sr0.75Ba0.25)5NiMn3O12, which constitutes the (, = 3, , = 2) member of the series, is made up of three face-sharing octahedra linked by one trigonal prism. For Sr9Ni2Mn5O21 (, = 2, , = 1) the sequence of polyhedra along the chains corresponds to a motif consisting of two octahedra,one trigonal prism,three octahedra,one trigonal prism. The manganese atoms occupy the octahedral sites in both phases, while the Ni2+ cations are distributed in the trigonal-prismatic sites in a disordered way. Only a small fraction of these (close to 20%) is located at the centres of the trigonal prisms, 80% being displaced towards the rectangular faces of the polyhedra and giving rise to a square-planar-like coordination. Both oxides present twinned microstructures, as evidenced by SAED and HREM. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Cost-Efficient Metal,Ceramic Composites,Novel Foam-Preforms, Casting Processes and Characterisation,ADVANCED ENGINEERING MATERIALS, Issue 3 2010Gisela Standke Because of their dissatisfactory cost-performance ratio metal matrix composites (MMCs) are still not established in industry, although they show improved properties compared to pure metals in some application fields. The present paper describes the development of enhanced MMCs based on silicon carbide (SiC) foams made by the Schwartzwalder process. Therefore, foams with cell sizes of 30, 45 and 60,ppi based on pressure less sintered SiC (SSiC) were developed. They were coated with layers of coarse SiC particles, which form a rough strut surface. The ceramic content of the foams could be increased to values of 20,30,mass%. Additionally, foam preforms based on clay-bonded SiC (as they are known from molten metal infiltration) were tested. The preforms were infiltrated with aluminium alloys AlSi9Cu3 and AlSi7Mg0.6 and cast iron EN-GJSA-XNiCr35-5-2 and EN-GJL-250. For aluminium alloys high pressure die casting (HPC) as well as gravity casting was applied, whereas iron was only infiltrated by gravity casting. For HPC an excellent interlocking of metal and preform was observed because of the microporosity of the rough surface of the SSiC foam struts. By the use of gravity casting preform cells up to 45,ppi could be well infiltrated. Microporosity in the ceramic coating and the typical hollow struts of the foams did not show metal infiltration. Even by use of moderate ceramic volume fractions pressure-infiltrated aluminium matrix composites showed a high specific stiffness of up to E/,,=,42,GPa,cm3,g,1 compared to conventional Al or Mg alloys (E/,,=,25,27,GPa,cm3,g,1). Ceramic foam based MMCs produced by pressure less casting showed no advantages in mechanical properties compared to pure metals. Nevertheless it can be expected that they can provide improved wear resistance and lower thermal expansion coefficients. [source] Synthesis, Characterisation and Nonlinear Optical Properties of Two-Dimensional Octupolar Systems Based on Phthalocyanine CompoundsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 18 2005Maurizio Quintiliani Abstract Four phthalocyanine-based compounds with pseudo D3h symmetry have been synthesised and fully characterised. Palladium cross-coupling methodologies were employed in order to synthesise 1,3,5-tris[(phthalocyaninyl)ethenyl]benzene (Heck) and 1,3,5-tris[(phthalocyaninyl)ethynyl]benzene (Sonogashira) derivatives. Knoevenagel condensation conditions were then applied to the synthesis of 1,3,5-tris[cyano(phthalocyaninyl)ethenyl]benzene and 2,4,6-tris[(phthalocyaninyl)ethenyl]-1,3,5-triazine. Preliminary second-order nonlinear optical studies, by hyper-Rayleigh scattering measurements, revealed that the compounds containing ethenyl linkers induce a strong octupolar effect while the ethynyl-containing compound does not show any octupolar enhancement. The introduction of a triazine central core does not modify significantly the nonlinear optical behaviour of the compound. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Synchrotron-Based Micro-CT and Refraction-Enhanced Micro-CT for Non-Destructive Materials Characterisation,ADVANCED ENGINEERING MATERIALS, Issue 6 2009Bernd R. Müller Abstract X-ray computed tomography is an important tool for non-destructively evaluating the 3-D microstructure of modern materials. To resolve material structures in the micrometer range and below, high brilliance synchrotron radiation has to be used. The Federal Institute for Materials Research and Testing (BAM) has built up an imaging setup for micro-tomography and -radiography (BAMline) at the Berliner storage ring for synchrotron radiation (BESSY). In computed tomography, the contrast at interfaces within heterogeneous materials can be strongly amplified by effects related to X-ray refraction. Such effects are especially useful for materials of low absorption or mixed phases showing similar X-ray absorption properties that produce low contrast. The technique is based on ultra-small-angle scattering by microstructural elements causing phase-related effects, such as refraction and total reflection. The extraordinary contrast of inner surfaces is far beyond absorption effects. Crack orientation and fibre/matrix debonding in plastics, polymers, ceramics and metal-matrix-composites after cyclic loading and hydro-thermal aging can be visualized. In most cases, the investigated inner surface and interface structures correlate to mechanical properties. The technique is an alternative to other attempts on raising the spatial resolution of CT machines. [source] Characterisation and Modelling of Non-Isothermal Precipitation in Metallic Systems,ADVANCED ENGINEERING MATERIALS, Issue 12 2006A. Deschamps During the process of most age hardening metallic alloys, non-isothermal precipitation plays a key role. The non-isothermal nature of precipitation processes can be either imposed by constraints of the process route (e.g. precipitation during coiling of NbC in steels, or precipitation in weld heat affected zones), or it can be found as the optimal pathway to the desired properties (e.g. multi-step heat treatments of aluminium alloys). The presented work addresses both on an experimental and on a modelling point of view some of these effects, both in aluminium alloys (the Al-Zn-Mg and Al-Zr-Sc systems) and in a Fe-Cu alloy. [source] Functional Characterisation of the Volume-Sensitive Anion Channel in Rat Pancreatic ,-CellsEXPERIMENTAL PHYSIOLOGY, Issue 2 2001L. Best The whole-cell and perforated patch configurations of the patch-clamp technique were used to characterise the volume-sensitive anion channel in rat pancreatic ,-cells. The channel showed high permeability (P) relative to Cl, to extracellular monovalent organic anions (PSCN/PCll= 1.73, Pacetate/PCll= 0.39, Plactate/PCll= 0.38, Pacetoacetate/PCll= 0.32, Pglutamate/PCll= 0.28) but was less permeable to the divalent anion malate (Pmalate/PCll= 0.14). Channel activity was inhibited by a number of putative anion channel inhibitors, including extracellular ATP (10 mM), 1,9-dideoxyforskolin (100 ,M) and 4-OH tamoxifen (10 ,M). Inclusion of the catalytic subunit of protein kinase A in the pipette solution did not activate the volume-sensitive anion channel in non-swollen cells. Furthermore, addition of 8-bromoadenosine 3,,5,-cyclic monophosphate (8-BrcAMP) or forskolin failed to activate the channel in intact cells under perforated patch conditions. Addition of phorbol 12,13-dibutyrate (200 nM), either before or after cell swelling, also failed to affect channel activation. Our findings do not support the suggestion that the volume-sensitive anion channel in pancreatic ,-cells can be activated by protein kinase A. Furthermore, the ,-cell channel does not appear to be subject to regulation via protein kinase C. [source] | |||||||||||||||||||||||||||||||||||||||||||||||||