Applied Organometallic Chemistry via MedWorm.com

Edited By Martin Oestreich The Mizoroki-Heck Reaction John Wiley & Sons, 2009, 608 pp. 115 euro (hardback) ISBN 978-0-470-03394-4

Applied Organometallic Chemistry — Wed, 17 Mar 2010 00:00:00 +0100

No Abstract. (Source: Applied Organometallic Chemistry)

Palladium-catalyzed cyanation reaction of aryl halides using K4[Fe(CN)6] as non-toxic source of cyanide under microwave irradiation

Applied Organometallic Chemistry — Sat, 13 Mar 2010 00:00:00 +0100

An efficient method for preparation of aryl nitriles - using [Pd{C6H2(CH2CH2 NH2)-(OMe)2,3,4} (µ-Br)]2 complex as an efficient catalyst and K4[Fe(CN)6] as a green cyanide source - from aryl bromides, aryl iodides and aryl chlorides under microwave irradiation has been reported. This complex has been demonstrated to be an active and efficient catalyst for this reaction. Using a catalytic amount of this synthesized palladium complex in DMF at 130 °C led to production of the cyanoarenes in excellent yields in short reaction times. Copyright © 2010 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Hetero- and homo-leptic Ru(II) catalyzed synthesis of cyclic carbonates from CO2; Synthesis, spectroscopic characterization and electrochemical properties

Applied Organometallic Chemistry — Fri, 12 Mar 2010 00:00:00 +0100

Based on the a ligand BDPPZ [(9a,13a-dihydro-4,5,9,14-tetraaza-benzo[b]triphenylene-11-yl)-phenyl-methanone] (1) and its polypyridyl hetero- and homoleptic Ru(II) metal complexes, [Ru(bpy)2L](PF6)2 (2), [Ru(phen)2L](PF6)2 (3), [Ru(dafo)2L](PF6)2 (4), [Ru(dcbpy)2L](PF6)2 (5) and [RuL3](PF6)2 (6) (where, L = ligand, bpy = 2,2[prime]-bipyridine, phen = 1,10-phenantroline, dafo = 4,5-diazafluoren-9-one and dcbpy = 3,3[prime]-dicarboxy-2,2[prime]-bipyridine), have been synthesized and characterized by elemental analysis, UV-vis, FT-IR, 1H and 13C-NMR spectra (for ligand), molar conductivity measurements and X-ray powder techniques. The electrochemical parameters of the substituted ligand and its polypyridyl hetero- and homoleptic Ru(II) metal complexes are reported by cyclic voltammetry. UV-vis...

Synthesis, characterization and single crystal structure determination of aluminum alkoxydisilanolates: precursors for silica-alumina composite

Applied Organometallic Chemistry — Sat, 06 Mar 2010 00:00:00 +0100

Several novel aluminum alkoxydisilanolate complexes were prepared by reaction of triphenylsilanol with aluminum 2-methoxyethoxide, aluminum 2-ethoxyethoxide, aluminum sec-butoxide and aluminum iso-propoxide. All new complexes, [(Ph3SiO)2Al(OR)]2 [where R = CH2CH2OCH3 (1), CH2CH2OC2H5 (2), CH(CH3)CH2CH3 (3) and CH(CH3)2 (4)] were characterized by elemental analysis, mass spectrometry and infrared spectroscopy (IR), as well as 1H, 13C, 29Si and 27Al NMR spectroscopies. The solid-state structures of the representative compound 2 and 4 were also verified by single-crystal X-ray analyses. Complexes 2 and 4 are dimers having distorted trigonal bipyramidal and tetrahedral coordination at the aluminum center, respectively. The 27Al NMR spectrum of compound 2 showed that the solid-state structure o...

Purification-chemical structure-electrical property relationship in gold nanoparticle liquids

Applied Organometallic Chemistry — Fri, 05 Mar 2010 00:00:00 +0100

Macroscopic assemblies of nanoparticles with fluid like characteristics, i.e. nanoparticle liquids (NPLs), are a new class of materials that exhibit unique properties compared with dispersions of nanoparticles in a molecularly distinct matrix phase. By focusing on reaction ratios, techniques to maximize concentration of reactants and quantification of chemical content during washing steps, a high degree of control over the purity of NPLs was maintained while allowing for easy scalability in batch sizes and synthesis throughput. A range of tertiary amines and quaternary ammoniums were used to successfully synthesize Au NPLs from a range of Au nanoparticles with nominal diameters from 6 to 20 nm and initially stabilized with either citrate or dodecanethiol. Stable Au NPLs after purification ...

Ruthenium(II) complexes incorporating tridentate Schiff base ligands: synthesis, spectroscopic, redox, catalytic and biological properties

Applied Organometallic Chemistry — Thu, 04 Mar 2010 00:00:00 +0100

A series of new diamagnetic ruthenium(II) complexes of the type [RuCl(CO)(B)(L)] (where B = PPh3, AsPh3 or Py; L = monobasic tridentate Schiff base ligands derived from o-aminophenol or o-aminothiophenol with ethylacetoacetate or ethylbenzoylacetate) have been synthesized and these complexes were characterized by physico-chemical and spectroscopic methods. Cyclic voltammograms of all the complexes show quasi-reversible oxidation in the range 0.24-1.05 V and the quasi-reversible reduction in the range - 0.14 to - 0.51 V. The observed redox potentials show little variation with respect to the replacement of triphenyl phosphine/arsine by pyridine. The complexes were tested as catalysts in the oxidation of primary and secondary alcohols using molecular oxygen at room temperature and also in C[...

Carbonyl group-containing organometallic intramolecular-coordination five-membered ring compounds

Applied Organometallic Chemistry — Wed, 03 Mar 2010 00:00:00 +0100

are easily synthesized by the following five reaction methods: (1) cyclometalation, especially, orthometalation reactions; (2) the reactions of the moieties of an unsaturated carbon[bond]carbon bond attached to a carbonyl group (C[triple bond]C[bond]CO, C[double bond]C[bond]CO); (3) the reactions of an unsaturated carbon[bond]carbon bond with carbon monoxide (C[triple bond]C and CO, C[double bond]C and CO); (4) carbonylative ring expansion reactions; and (5) others. These compounds are very easily and regio-specifically synthesized with many kinds of metal compounds, including both transition metals and main group metals. Many of such the reactions are easily applied to organic syntheses. Copyright © 2010 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Two synthesis routes of organometallic precursors for the elaboration of SiCNYO pre-alloyed nanopowders

Applied Organometallic Chemistry — Tue, 02 Mar 2010 00:00:00 +0100

Two routes were simultaneously investigated to prepare organometallic precursors. They were characterized by NMR and FTIR techniques. In the first route, yttrium acetate was silylated by trimethylchlorosilane before its dissolution in hexamethydisilazane. That leads to a liquid precursor containing Si[bond]C[bond]N[bond]Y[bond]O[bond]H elements. In the second route, a precursor with the same elements was elaborated by dissolution of an amminolysed yttrium compound in tetramethyldisiloxane. The amminolysed yttrium compound was obtained through the amminolysis of the yttrium trichloride by triethylamine [N(C2H5)3]. Copyright © 2010 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Hybrids of hybrids: nano-scale combinations of polyphosphazenes with other materials

Applied Organometallic Chemistry — Tue, 02 Mar 2010 00:00:00 +0100

This article is a review of recent developments in the author's laboratory to combine polyphosphazenes with other materials in order to generate new combinations of useful properties. Copyright © 2010 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Dibutyltin oxide catalyzed aminolysis of oxalate to carbamate, oxamate and derivatives of imidazolidine trione

Applied Organometallic Chemistry — Tue, 02 Mar 2010 00:00:00 +0100

Catalytic aminolysis of oxalates by simple and substituted ureas has been shown to give carbamates, oxamates and derivatives of imidazolidine trione. Various substituted ureas and oxalates were screened to verify the applicability of the protocol. The role of dibutyltin oxide as catalyst, effect of solvent and reaction conditions on product distribution pattern has been discussed. Copyright © 2010 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Exploration of amino-functionalized ionic liquids as ligand and base for Heck reaction

Applied Organometallic Chemistry — Tue, 02 Mar 2010 00:00:00 +0100

A kind of amino-functionalized ionic liquid has been prepared and investigated as ligand and base for the Heck reactions between aryl iodides and bromides with olefins in the presence of a catalytic amount of Pd submicron powder in [Bmim]PF6. The reactions generated the corresponding products in excellent yields under mild reaction conditions. The generality of this catalytic system to the different substrates also gave satisfactory results. The key feature of the reaction is that Pd species and ionic liquids were easily recovered and reused six times with constant activity. Copyright © 2010 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Synthesis and antimicrobial activities of sulfonohydrazide-substituted 8-hydroxyquinoline derivative and its oxinates

Applied Organometallic Chemistry — Thu, 25 Feb 2010 00:00:00 +0100

Looking at the pharmacological importance of 8-hydroxyquinolines and sulfonamides, in the present study, a novel bi-dentate ligand 4-amino-N[prime]-[(8-hydroxyquinoline-5-yl)methyl] benzenesulfonohydrazide (AHQMBSH) having above both moieties within a single molecular framework was synthesized by the reaction of N-acetamidobenzene sulfonohydrazide with 5-chloromethyl-8-hydroxyquinoline hydrochloride. Its metal(II) oxinates were also prepared with Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) salts. All the above compounds were investigated by physicochemical analyses, thermogravimetric analysis and spectroscopic techniques. Antimicrobial activities for the above prepared compounds were carried out using the agar-plate method against various strains of bacteria (Staphylococcus aureus, B...

Synthesis and microwave-assisted catalytic activity of novel bis-benzimidazole salts bearing furfuryl and thenyl moieties in Heck and Suzuki cross-coupling reactions

Applied Organometallic Chemistry — Wed, 24 Feb 2010 00:00:00 +0100

A mixture of bis-benzimidazole salts (1-7), Pd(OAc)2 and K2CO3 in DMF [bond]H2O catalyzes, in high yield, the Suzuki and Heck cross-coupling reactions assisted by microwave irradiation in a short time. In particular, the yields of the Heck and Suzuki reactions with aryl bromides were found to be nearly quantative. The synthesized bis-benzimidazole salts (1-7) were identified by 1H[bond]13C NMR, IR spectroscopic methods and micro analysis. Copyright © 2010 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Ethanol-promoted reductive homocoupling reactions of aryl halides catalyzed by palladium on carbon (Pd/C)

Applied Organometallic Chemistry — Wed, 24 Feb 2010 00:00:00 +0100

Homocoupling reactions of aryl bromides or iodides proceeded smoothly with palladium on carbon (Pd/C) catalyst, ethanol and base in dimethyl sulfoxide (DMSO) to afford exclusively symmetric biaryls in good to excellent yields. Ethanol was first used as a reducing agent in situ to reduce the Pd2+/C species into Pd0/C active species to complete the catalytic redox cycle. It was found that ethanol can promote the Pd/C-catalyzed reductive homocoupling of aryl iodides and bromides efficiently in the presence of base. A reaction mechanism has been put forward and discussed. Copyright © 2010 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Edited By Jacob Zabicky The Chemistry of Metal Enolates - Part 1 Wiley, 2009, 577 pp. (part 1; 1250 pp., parts 1 and 2) (parts 1 and 2; hardback) ISBN 978-0-470-06168-8

Applied Organometallic Chemistry — Wed, 24 Feb 2010 00:00:00 +0100

No Abstract. (Source: Applied Organometallic Chemistry)

The synthesis and properties of nanoscale ionic materials

Applied Organometallic Chemistry — Wed, 17 Feb 2010 00:00:00 +0100

In this article we discuss the effect of constituents on structure, flow, and thermal properties of nanoscale ionic materials (NIMs). NIMs are a new class of nanohybrids consisting of a nanometer-sized core, a charged corona covalently attached to the core, and an oppositely charged canopy. The hybrid nature of NIMs allows for their properties to be engineered by selectively varying their components. The unique properties associated with these systems can help overcome some of the issues facing the implementation of nanohybrids to various commercial applications, including carbon dioxide capture, water desalinization and as lubricants. Copyright © 2010 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Indazaboles - synthesis and molecular structure

Applied Organometallic Chemistry — Wed, 17 Feb 2010 00:00:00 +0100

The reaction of 1-trimethylsilyl-indazole with boranes affords indazaboles accompanied by elimination of trimethysilane. Thus, the two isomers of parent indazabole are formed in a 1:1 ratio using borane in THF (BH3/THF), characterized by NMR spectroscopy in solution (1H, 11B and 13C NMR). In contrast, the analogous reaction with 1,2-bis(tetramethylene)diborane(6) proceeds to give a single isomer of the B-alkylated indazabole via symmetric ring cleavage of the diborane(6), as shown by NMR in solution and X-ray structural analysis in the solid state. The molecular structure is fluxional in solution. In the solid state, the central B2N4 ring adopts a distorted boat conformation. Calculated gas phase geometries of the parent indazaboles and of the B-alkylated indazabole were optimized by DFT m...

Synthesis and anticancer activity of chalcogenide derivatives and platinum(II) and palladium(II) complexes derived from a polar ferrocene phosphanyl-carboxamide

Applied Organometallic Chemistry — Wed, 17 Feb 2010 00:00:00 +0100

The polar phosphanyl-carboxamide, 1[prime]-(diphenylphosphanyl)-1-[N-(2-hydroxyethyl)carbamoyl]ferrocene (1), reacts readily with hydrogen peroxide and elemental sulfur to give the corresponding phosphane-oxide and phosphane-sulfide, respectively, and with platinum(II) and palladium(II) precursors to afford various bis(phosphane) complexes [MCl2(1-[kappa]P)2] (M = trans-Pd, trans-Pt and cis-Pt). The anticancer activity of the compounds was evaluated in vitro with the complexes showing moderate cytotoxicities towards human ovarian cancer cells. Moreover, the biological activity was found to be strongly influenced by the stereochemistry, with trans-[PtCl2(1-[kappa]P)2] being an order of magnitude more active than the corresponding cis isomer. Copyright © 2010 John Wiley & Sons, Ltd. (Source...

Enantioselective alkynylation of aldehydes catalyzed by a camphor sulfonylated amino alcohols titanium(IV) catalyst system

Applied Organometallic Chemistry — Sat, 06 Feb 2010 00:00:00 +0100

A new titanium(IV) complex has been developed for the effective enantioselective alkynylation of phenylacetylene addition to aldehydes. The titanium(IV) complex was readily prepared in situ from (R)-C-(7,7-dimethyl-2-oxo-bicyclo[2.2.1]hept-1-yl)-(1R,2S)-N-(2-hydroxy-1,2-diphenyl-ethyl)-methanesulfonamide (1h) and tetraisopropyl titanate [Ti(i-OPr)4]. A variety of aromatic aldehydes and [alpha],[beta]-unsaturated aldehydes were found to be suitable substrates in the presence of the camphor sulfonylated amino alcohol titanium(IV) complex [10 mol% 1h, 40 mol% Ti(i-OPr)4]. The desired propargylic alcohols were afforded with high isolated yields (up to 90%) and moderate enantioselectivities (up to 65% ee) under mild conditions. Copyright © 2010 John Wiley & Sons, Ltd. (Source: Applied Organome...

Synthetic, spectral as well as in vitro antimicrobial studies on some bismuth(III) bis(N,N-dialkyldithiocarbamato) alkylenedithiophosphates

Applied Organometallic Chemistry — Fri, 29 Jan 2010 00:00:00 +0100

Mixed sulfur donor ligand complexes of the type bismuth(III) bis(N,N-dialkyldithiocarbamato) alkylenedithiophosphate, [R2NCS2]2BiS2 [where R = CH3 and C2H5; G = -CH2-C(C2H5)2-CH2-, -CH2-C(CH3)2-CH2-, -CH(CH3)-CH(CH3)- and -C(CH3)2-C(CH3)2-] were synthesized in 1:1 molar ratio of bismuth(III) bis(N,N-dialkyldithiocarbamate) chloride and ammonium alkylenedithiophosphate in refluxing benzene and characterized by melting point, molecular weight determinations, elemental analysis (C, H, N, Bi and S) and spectral [UV, IR,NMR (1H,13C and 31P) and powder X ray diffraction] studies; all these studies were in good agreement with the synthesized complexes. These newly synthesized derivatives are yellow and brown colored solids and are soluble in common organic solvents like benzene, chloroform, dichl...

In-vitro antimicrobial, thermal and spectral studies of mixed ligand Cu(II) heterochelates of clioquinol and coumarin derivatives

Applied Organometallic Chemistry — Sat, 23 Jan 2010 00:00:00 +0100

The mixed-ligand heterochelates of Cu(II) with 5-chloro-7-iodo-8-hydroxyquinoline (clioquinol) and various uninegative bidentate ligands were prepared. The structure of mixed-ligand heterochelates was investigated using spectral, physicochemical, elemental analysis and thermal studies. The FAB-mass spectrum of [Cu(A2)(CQ)(H2O)2].2H2O has been carried out. Magnetic moment and reflectance spectral studies reveal that an octahedral geometry has been assigned to all the prepared heterochelates. The kinetic parameters such as order of reaction (n), the energy of activation (Ea), the pre-exponential factor (A), the activation entropy ([Delta]S#), the activation enthalpy ([Delta]H#) and the free energy of activation ([Delta]G#) have been reported. The ligands, metal salts, heterochelates, control...

Synthesis of [pi]-conjugated polymers via regioregular organometallic polymers 2. Transformation of titanacyclopentadiene- containing polymer into poly(p-phenylene) derivative

Applied Organometallic Chemistry — Fri, 22 Jan 2010 00:00:00 +0100

The transformation of a regioregular organometallic polymer possessing titanacyclopentadiene-2,5-diyl units into a poly(p-phenylene) derivative by means of a novel polymer reaction method is described. The organotitianium polymer was prepared by the polymerization of 1,4-diethynyl-2,5-dioctyloxybenzene and a low-valent titanium complex, generated in situ from titanium(IV) isopropoxide and isopropylmagnesium chloride, and was subjected to the reaction with 3-bromo-1-propyne followed by the protonation. Consequently, a polymer consisting of the substituted phenylene-1,4-diyl units could be produced in a high yield, which is soluble in organic solvents such as chloroform. The number-average molecular weight and the molecular weight distribution of the polymer were estimated as 4800 and 1.8, r...

Edited by Christian Bruneau and Pierre H. Dixneuf Metal vinylidenes and allenylidenes in catalysis: from reactivity to applications in synthesis Wiley-VCH, 2008, 338 pp. (hardback) ISBN-10 3-527-31892-5 ISBN-13 978-3-527-31892-6

Applied Organometallic Chemistry — Fri, 22 Jan 2010 00:00:00 +0100

No Abstract. (Source: Applied Organometallic Chemistry)

Preparation of planar-chiral multidonor phosphanylferrocene carboxamides and their application as ligands for palladium-catalysed asymmetric allylic alkylation

Applied Organometallic Chemistry — Fri, 22 Jan 2010 00:00:00 +0100

Amide coupling of (Sp)-2-(diphenylphosphanyl)ferrocene-1-carboxylic acid with appropriate terminal amines mediated by 1-hydroxybenzotriazole and a carbodiimide affords multi-donor amides terminally functionalized with planar-chiral (Sp)-2-(diphenylphosphanyl)ferrocen-1-yl moieties in good to excellent yields. Palladium catalysts based on these ligands efficiently promote asymmetric allylic alkylation of 1,3-diphenylallyl acetate with in situ generated dimethyl malonate anion to give the C-alkylated product with ees up to 93% at room temperature. Copyright © 2010 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

The influence of halogen anions and N-ligands in CuXn/N-ligands on the catalytic performance in oxidative carbonylation of methanol

Applied Organometallic Chemistry — Fri, 22 Jan 2010 00:00:00 +0100

The catalytic properties of CuXn/N-ligands (X = Cl, Br and I; n = 1 or 2) in oxidative carbonylation of methanol were investigated. It was found that the interaction of halogen anions, N-ligands and Cu (I) affected the catalytic performance of copper complex catalyst in the reaction, especially iodide anion and 1,10-phenanthroline (Phen). When CuI/Phen was used as a catalyst, the conversion of methanol was 42.6%, the selectivity to dimethyl carbonate was 99.2% and the TOF was 13.1 h-1 at an optimized conditions: CuI/Phen 0.2 mol l-1, 120 °C, 2 h, 2.4 MPa, PCO/PO2 = 2:1. Compared with the plain CuI catalyst, the catalytic activity of CuI/Phen increased about 36 times. When CuI/Phen catalyst was immobilized on polystyrene (PS), the heterogenized catalyst, CuI/Phen-NH-PS, also exhibited very...

Studies on the synthesis and thermal properties of alkoxysilane-terminated organosilicone dendrimers

Applied Organometallic Chemistry — Wed, 06 Jan 2010 00:00:00 +0100

Silicone core dendrimers bearing terminal dialkoxy and trialkoxy silane groups were prepared in a three-step synthesis. Initially, the Si[bond]H terminated multifunctional silicone dendrimer, i.e. tetrakis(dimethylsiloxy)silane, was prepared by the reaction of tetraethoxysilane and dimethylethoxysilane. Tetrakis(dimethylsiloxy)silane on reaction with allylglycidylether in the presence of Speier's catalyst under pressure (100 psi) yielded epoxy-terminated dendrimer in very high yield (95%). The epoxy-terminated dendrimer was reacted with aminopropylalkoxysilanes to yield the next-generation dendrimer bearing dialkoxy and trialkoxy silane groups. The dendrimers were characterized by the usual physico-chemical techniques, i.e. elemental analysis, FT-IR, 1H, 13C and 29Si NMR. Thermal studies (...

Iron oxide-based magnetic nanostructures bearing cytotoxic organosilicon molecules for drug delivery and therapy

Applied Organometallic Chemistry — Tue, 05 Jan 2010 00:00:00 +0100

The results of our own investigation on synthesis, physico-chemical and biological study of iron oxide based magnetic nanoparticles bearing cytotoxic organosilicon molecules of choline and colamine analogues, as potential agents for antitumor therapy, are summarized. These molecules contain hydrophilic head and long lipophilic tails, which are able to deepen inside the first surfactant shell (oleic acid), forming bilayer membrane like structures. Such compositions have a great privilege possessing magnetic properties, which in some cases could be essential moment in targeted drug delivery. The methodological approach has been developed and applied to the preparation of water soluble single or mixed coated biologically active nanoparticles of different types. Copyright © 2010 John Wiley & ...

Edited by Jean-Marie Basset, Rinaldo Psaro, Dominique Roberto and Renato Ugo Modern surface organometallic chemistry Wiley-VCH, 2009, 725 pp. (hardback) ISBN 978-3-527-31972-5

Applied Organometallic Chemistry — Tue, 05 Jan 2010 00:00:00 +0100

No Abstract. (Source: Applied Organometallic Chemistry)

Characterization of single-walled carbon nanotubes synthesized using iron and cobalt nanoparticles derived from self-assembled diblock copolymer micelles

Applied Organometallic Chemistry — Tue, 05 Jan 2010 00:00:00 +0100

We present a comparative study of single-walled carbon nanotubes grown using iron and cobalt nanoparticles as catalysts via the chemical vapor deposition approach. Monodispersed iron and cobalt oxide nanoparticles with an average size of 2 nm were prepared using a polystyrene-b-poly (4-vinylpyridine) diblock copolymermicelle template. The 2 nm iron oxide nanoparticles generated single-walled carbon nanotubes with an average diameter of 1.5 nm while 2 nm cobalt oxide nanoparticles produced single-walled carbon nanotubes with an average diameter of 1.0 nm. To achieve high growth yield using iron nanoparticles as catalyst, higher carbon feed rate is required. These findings demonstrate the importance of the synergic interaction between catalyst and carbon precursor in single-walled carbon nan...

Synthesis of poly(vinylene-arsine)s-stabilized silver nanoparticles

Applied Organometallic Chemistry — Tue, 05 Jan 2010 00:00:00 +0100

Stabilization of poly(vinylene-arsine)s (1) towards silver nanoparticles was carried out to estimate the coordination and protecting ability of phenyl-substituted poly(vinylene-arsine) (1a) and methyl-substituted poly(vinylene-arsine) (1b). In the presence of 1 in 1:1 ratio with AgNO3, colloidal solutions were obtained. The methyl-substituted poly(vinylene-arsine) (1b) is a better stabilizer for silver nanoparticles in N,N-dimethylformamide owing to its less bulky structure than the phenyl-substituted poly(vinylene-arsine) (1a). Copyright © 2010 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Efficient fuel cell catalysts emerging from organometallic chemistry

Applied Organometallic Chemistry — Tue, 05 Jan 2010 00:00:00 +0100

During the last few decades organometallic methodologies have generated a number of highly effective electrocatalyst systems based on mono- and bimetallic nanosparticles having controlled size, composition and structure. In this microreview we summarize our results in fuel cell catalyst preparation applying triorganohydroborate chemistry, 'reductive particle stabilization' using organoaluminum compounds, and the controlled decomposition of organometallic complexes. The advantages of organometallic catalyst preparation pathways are exemplified with Ru[bond]Pt nanoparticles@C as promising anode catalysts to be used in direct methanol oxidation fuel cells (DMFC) or in polymer electrolyte fuel cells (PEMFC) running with CO-contaminated H2 as the feed. Recent findings with highly efficient PtCo...

Copper-catalyzed/mediated aromatic C[bond]H bond functionalization

Applied Organometallic Chemistry — Tue, 05 Jan 2010 00:00:00 +0100

The C[bond]H functionalization strategy has received substantial attention because of its economic, sustainable and environmentally benign features. Most reports are on palladium, rhodium or ruthenium catalysis, and reports on copper catalysis are relatively fewer. Recently, many reports on copper-catalyzed/mediated C[bond]H functionalization have been published. Copper salts bear properties of cheapness and relatively low toxicity. This review introduces an advance on copper-catalyzed/mediated aromatic C[bond]H functionalization. The content includes aromatic ring C[bond]H bond functionalization and heteroaromatic C[bond]H bond functionalization forming new carbon-carbon or carbon-heteroatom bonds. Copyright © 2010 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Nickel(II) complexes bearing pyrazolylimine ligand: synthesis, structure, and catalytic properties for vinyl-type polymerization of norbornene

Applied Organometallic Chemistry — Wed, 30 Dec 2009 00:00:00 +0100

Two nickel(II) complexes of {2-[C3HN2(R1)2-3,5]}[C(R2)[double bond]N(C6H3iPr2-2,6)]NiBr2 (complex 1: R1 = CH3, R2 = 2,4,6-trimethylphenyl; complex 2: R1 = R2 = Ph) were synthesized and characterized. The solid-state structure of complex 1 has been confirmed by X-ray single-crystal analysis. Activated by methylaluminoxane (MAO), complexes 1 and 2 are capable of catalyzing the polymerization of norbornene with moderate activities [up to 10.56 × 105 gPNBE (mol Ni h)-1] with high molecular weights (Mw[les]13.56 × 105 g mol-1) and molecular weight distributions were around 2. The influences of polymerization parameters such as reaction temperature and Al-Ni molar ratio on catalytic activity and molecular weight of the polynorbornene were investigated in detail. The obtained polynorbornenes we...

Luminescent chiral organoboron 8-aminoquinolate-coordination polymers

Applied Organometallic Chemistry — Thu, 24 Dec 2009 00:00:00 +0100

We have successfully synthesized optically active organoboron aminoquinolate-based coordination polymers bearing the chiral side chain derived from L-alanine, and studied their optical behavior by UV-vis and photoluminescence spectroscopies. Higher absolute quantum yields ([Phi]F) of the obtained polymers, measured by integrating sphere method, were observed with electron-withdrawing substituent ([Phi]F = 0.80) than with electron-donating substituent ([Phi]F = 0.52). The circular dichroism (CD) study in the mixed solvents of CHCl3 and DMF showed that the secondary structures of the obtained polymers were stabilized by hydrogen-bonding interaction in the side chain. From concentration dependence on the CD spectra, the chirality of the obtained polymers originated from the nature of one mole...

An alternative CuCl-piperidine-catalyzed oxidative homocoupling of terminal alkynes affording 1,3-diynes in air

Applied Organometallic Chemistry — Wed, 23 Dec 2009 00:00:00 +0100

CuCl with the use of a catalytic amount of piperidine as additive shows high catalytic activity for the oxidative homocoupling reactions of terminal alkynes in toluene at 60 °C in air to afford 1,3-diynes in high yields. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Silicon nanoparticles with chemically tailored surfaces

Applied Organometallic Chemistry — Tue, 22 Dec 2009 00:00:00 +0100

Silicon nanoparticles are useful materials for optoelectronic devices, solar cells and biological markers. The synthesis of air-stable nanoparticles with tunable optoelectronic properties is highly desirable. The mechanochemical synthesis of silicon nanoparticles via high-energy ball milling produces a variety of covalently bonded surfaces depending on the nature of the organic liquid used in the milling process. The use of the C8 reactants including octanoic acid, 1-octanol, 1-octaldehyde and 1-octene results in passivated surfaces characterized by strong Si[bond]C bonds or strong Si[bond]O bonds. The surfaces of the nanoparticles were characterized by infrared spectroscopy and nuclear magnetic resonance spectroscopy. The nanoparticles were soluble in common organic solvents and remarkabl...

Synthesis, characterization and biological studies of oxovanadium(IV) complexes with triazole-derived Schiff bases

Applied Organometallic Chemistry — Thu, 17 Dec 2009 00:00:00 +0100

A series of triazole-derived Schiff bases (L1-L5) and their oxovanadium(IV) complexes have been synthesized. The chemical structures of Schiff bases were characterized by their analytical (CHN analysis) and spectral (IR, 1H and 13C NMR and mass spectrometry) data, and oxovanadium(IV) complexes were elucidated by their physical (magnetic susceptibility and conductivity), analytical (CHN analysis), conductance measurements and electronic spectral data. The molar conductivity data indicate the oxovanadium(IV) complexes to be non-electrolyte. The Schiff bases act as bidentate and coordinate with the oxovanadium(IV)-forming stoichiometry of a complex as [M (L-H)2] where M = VO and L = L1-L5 in a square-pyramidal geometry. The agar well diffusion method was used for in vitro antibacterial screen...

Bis(imino)pyridine palladium(II) complexes as efficient catalysts for the Suzuki-Miyaura reaction in water

Applied Organometallic Chemistry — Thu, 17 Dec 2009 00:00:00 +0100

Bis(imino)pyridine palladium(II) complexes 3 and 4 of type [PdCl(L)PF6] are found to be efficient catalysts for Suzuki-Miyaura reactions of aryl halides and arylboronic acids. The reactions proceed smoothly to generate the corresponding biaryl compounds in moderate to excellent yields. The synthesis of various fluorinated biphenyl derivatives was successfully achieved by the complex 4 catalyzed the Suzuki-Miyaura reaction in the presence of surfactants bearing a long alkyl chain. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Edited by Kuiling Ding and Yasuhiro Uozumi Handbook of Asymmetric Heterogeneous Catalysis Wiley-VCH, 2008, 448 pp. (hardcover) ISBN-10 3-527-31913-1 ISBN-13 978-3-527-31913-8

Applied Organometallic Chemistry — Thu, 17 Dec 2009 00:00:00 +0100

No Abstract. (Source: Applied Organometallic Chemistry)

Synthesis of 2-(N-arylimino)pyrrolide nickel complexes and polymerization of methyl methacrylate

Applied Organometallic Chemistry — Thu, 17 Dec 2009 00:00:00 +0100

The synthesis, characterization and methyl methacrylate polymerization behaviors of 2-(N-arylimino)pyrrolide nickel complexes are described. The nickel complex [NN]2Ni (1, [NN] = [2-C(H)NAr-5-tBu-C4H2N]-, Ar = 2,6-iPr2C6H3) was prepared in good yield by the reaction of [NN]Li with trans-[Ni(Cl)(Ph)(PPh3)2] in THF. Reaction of [NN]Li with NiBr2(DME) yielded the nickel bromide [NN]Ni(Br)[NNH] (2). Complexes 1 and 2 were characterized by 1H NMR and IR spectroscopy and elemental analysis, and by X-ray single crystal analysis. Both complexes, upon activation with methylaluminoxane, are highly active for the polymerization of methyl methacrylate to give high molecular weight polymethylmethacrylate with narrow molecular distributions. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Org...

Cyclodextrin inclusion complexes as novel MOCVD precursors for potential cobalt oxide deposition

Applied Organometallic Chemistry — Thu, 17 Dec 2009 00:00:00 +0100

The potential use of the inclusion complexes of [beta]-cyclodextrins with metal halides as novel precursors in MOCVD applications was examined in terms of microstructure, thermal stability and chemical modifications during heating. The investigation was especially focused on the inclusion complex of [beta]-cyclodextrin with cobalt iodide for cobalt oxide thin film deposition. The general composition assigned to the dextrin's inclusion complex was: ([beta]-CD)2[bull]CoI7[bull]11H2O. It was found that the inclusion complex of [beta]-cyclodextrin with CoI2 may prove a promising alternative to traditional metalorganic or organometallic Co-precursors for precise CVD applications. The sublimation temperature must be preferably in the range 70-125 °C, and the decomposition temperature (substrate...

New chiral phosphinite ligands with C2-symmetric axis and their possible applications in Ru-catalyzed asymmetric transfer hydrogenation

Applied Organometallic Chemistry — Thu, 17 Dec 2009 00:00:00 +0100

The new chiral ligands N,N[prime]-bis-[(1R)-1-ethyl-2-O-(diphenylphosphinite)ethyl]ethanediamide, 1, and N,N[prime]-bis-[(1S)-1-isobutyl-2-O-(diphenylphosphinite)ethyl]ethanediamide, 2, and the corresponding ruthenium complexes 3 and 4 were prepared and their structures were elucidated by a combination of multinuclear NMR spectroscopy, IR spectroscopy and elemental analysis. Following activation by NaOH, these chiral ruthenium complexes serve as catalyst precursors for the asymmetric transfer hydrogenation of acetophenone derivatives in iPrOH. The complexes 3 and 4 showed high catalytic activity but low selectivity in asymmetric transfer hydrogenation reactions. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

C[bond]H bond functionalization of aromatic heterocycles with chelating dicarbene palladium(II) and platinum(II) complexes

Applied Organometallic Chemistry — Thu, 17 Dec 2009 00:00:00 +0100

Chelating dicarbene complexes of palladium(II) and platinum(II) catalyse at room temperature with 1% catalyst loading the reaction of ethyl phenylpropiolate with aromatic heterocycles to yield synthetically useful intermediates for fine chemicals without the need to use prefunctionalized substrates. The reaction outcome was found to be strongly dependent on the nature of the anionic ligands at the metal complex. Addition of silver salts to replace halide ligands with more weakly coordinating anions improves the reaction yield and changes the product distributions: heterocycle[bond]alkyne 2:1 adducts are obtained together with the usual hydroarylation products, which potentially broadens the scope of the reaction. The nature of the employed heterocycle, in particular its steric characterist...

Reduction of nitroarenes followed by propanol group transfer from tris(3-hydroxypropyl)- amine and cyclization leading to quinolines under heterogeneous Pd[bond]C catalysis

Applied Organometallic Chemistry — Thu, 17 Dec 2009 00:00:00 +0100

Nitroarenes having electron-donating or -withdrawing substituents are reduced to anilines and cyclized with tris(3-hydroxypropyl)amine in the presence of a catalytic amount of Pd[bond]C along with tin(II) chloride and isopropanol in dioxane-H2O medium to give the corresponding quinolines in good to excellent yields. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Long-chain silanes as reducing agents part 1: a facile, efficient and selective route to amine and phosphine-stabilized active Pd-nanoparticles

Applied Organometallic Chemistry — Thu, 17 Dec 2009 00:00:00 +0100

Recently, metal nanoparticles have found applications in various fields, which have necessitated exploration of new avenues to obtain such materials. In this publication, a hydrosilane-based reduction and characterization of resulting palladium nanoparticles is achieved using palladium acetate as nanoparticle precursor and octadecylsilane as a reducing agent. The influence of phosphine and amine ligands in the stabilization of nanoparticles is also investigated. In addition, a brief mechanistic proposal of the reduction process is also discussed. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Binuclear Ru(III) Schiff base complexes: synthesis, spectral characterization, oxidation, C[bond]C coupling reactions and antibacterial activities

Applied Organometallic Chemistry — Thu, 17 Dec 2009 00:00:00 +0100

New hexa-coordinated binuclear Ru(III) Schiff base complexes of the type {[(B)2X2Ru]2L} (where B = PPh3 or AsPh3; X = Cl or Br; L = binucleating N2O2 Schiff bases) were synthesized and characterized by elemental analysis, magnetic susceptibility measurement, FT-IR, UV-vis, 13C{1H}-NMR, ESR at 300 and 77 K, cyclic voltammetric technique, powder X-ray diffraction pattern and SEM. The new complexes were used as catalysts in phenyl-phenyl coupling reaction and the oxidation of alcohols to their corresponding carbonyl compounds using molecular oxygen atmosphere at room temperature. Further, the new Schiff base ligands and their Ru(III) complexes were also screened for their antibacterial activity against K. pneumoniae, Shigella sp., M. luteus, E. coli and S. typhi. From this study, it was found...

Reactivity of organosilicon precursors in remote hydrogen microwave plasma chemical vapor deposition of silicon carbide and silicon carbonitride thin-film coatings

Applied Organometallic Chemistry — Thu, 17 Dec 2009 00:00:00 +0100

A number of organosilicon precursors for silicon carbide and silicon carbonitride thin-film coatings, such as silanes, carbosilanes, aminosilanes, and disilazane, respectively, were characterized in terms of their reactivity in a remote microwave plasma chemical vapor deposition process, which was induced using hydrogen as plasma generating gas. The process displayed high selectivity with respect to the activating species and the chemical bonds in the molecular structure of the precursors. In view of very short life times of excited hydrogen plasma species the activation step takes place with an exclusive contribution of ground-state hydrogen atoms. The C[bond]H, C[bond]C, Si[bond]C, Si[bond]N, C[bond]N and N[bond]H bonds present in the molecules of the precursors are non-reactive and only...

Efficient synthesis of conjugated alkynyl cycloalkenones: Pd(PPh3)4-AgOAc- catalyzed direct coupling of 1-alkynes with 3-oxocycloalkenyl triflates

Applied Organometallic Chemistry — Thu, 17 Dec 2009 00:00:00 +0100

Palladium - silver acetate-catalyzed cross coupling of vinyl triflates and 1-alkynes was investigated. This strategy offered a very straightforward and efficient method for access to conjugated alkynyl cycloalkenones from the conjugated vinyl triflates and 1-alkynes. Moreover, the triflates derived from 1,3-cycloalkadione needed no further purification and could be reacted immediately with 1-alkynes to provide the conjugated alkynyl cycloalkenones in excellent overall yields. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Novel methodologies for the synthesis of functionalized lipophilic carboranes

Applied Organometallic Chemistry — Thu, 17 Dec 2009 00:00:00 +0100

Novel synthetic protocols for the synthesis of lipophilic carboranes were developed utilizing two C[bond]C bond forming reactions, namely Baylis-Hillman and enynedioate cycloaddition reactions. Some of these carboranes were converted into further functionalized carboranes via nucleophilic allylic isomerization. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Organocatalytic synthesis of cyanohydrin trimethylsilyl ethers by potassium 4-benzylpiperidinedithiocarbamate under solvent-free conditions

Applied Organometallic Chemistry — Thu, 17 Dec 2009 00:00:00 +0100

Potassium 4-benzylpiperidinedithiocarbamate was found to be an efficient organocatalyst for facile addition of trimethylsilyl cyanide to a wide variety of aldehydes and ketones to afford corresponding cyanohydrin trimethylsilyl ethers in high to quantitative yields. The reaction proceeded smoothly by employing 2.0 mol% PBPDC loading under mild conditions at room temperature within a very short reaction time. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Synthesis, characterization, electrochemical, catalytic and antimicrobial activity studies of hydrazone Schiff base ruthenium(II) complexes

Applied Organometallic Chemistry — Thu, 17 Dec 2009 00:00:00 +0100

Four tridentate O, N, O donor Schiff base ligands were prepared by the reaction of substituted benzhydrazide and appropriate salicylaldehyde. The complexes of these ligands were synthesized by refluxing the ligands with ruthenium(II) starting complexes of the formula [RuHCl(CO)(EPh3)2B] in benzene, where E = P or As; B = PPh3 or AsPh3 or pyridine. The newly synthesized complexes were characterized by elemental, spectral (FT-IR, UV and NMR) and electrochemical data. On the basis of the above studies, an octahedral structure has been proposed for all the complexes. The catalytic efficiency of the complexes in aryl-aryl couplings and oxidation of alcohols was examined and their inhibition activity against the growth of the micro-organisms was also examined. Copyright © 2009 John Wiley & Sons...

A facile route to ruthenium-carbene complexes and their application in furfural hydrogenation

Applied Organometallic Chemistry — Tue, 08 Dec 2009 00:00:00 +0100

A number of new N-heterocyclic carbene (NHC) ligands were synthesized via a multicomponent reaction, wherein an aldehyde or ketone, a primary amine and an [alpha]-acidic isocyanide were reacted, giving the corresponding 2H-2-imidazolines. These were easily alkylated with an alkyl halide at position N-3, yielding the final NHC precursors, that were then complexed with Ru in situ. The resulting complexes are shown to be active and selective catalysts for the transfer hydrogenation of furfural to furfurol, using isopropanol as the hydrogen source. Importantly, the carbene ligand remains coordinated to the ruthenium center throughout the reaction. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Fluoride catalyzed rearrangements of polysilsesquioxanes, mixed Me, vinyl T8, Me, vinyl T10 and T12 cages

Applied Organometallic Chemistry — Fri, 04 Dec 2009 00:00:00 +0100

Insoluble mixtures of polyvinylsilsesquioxane, -(vinylSiO1.5)n- PVS, and polymethylsilsesquioxanes, -(MeSiO1.5)n- PMS, in THF at ambient when treated with catalytic amounts (1-5 mol%) of fluoride ion introduced as tBu4 NF will depolymerize and dissolve. The resulting soluble species consist of [vinylxMe8-x(SiO1.5)]8, [vinylxMe8-x(SiO1.5)]10 and [vinylxMe8-x(SiO1.5)]12. Ratios of 1:1 of PVS:PMS greatly favor formation of vinyl rich cages. Only at ratios of 1:5 are the proportions of vinyl:Me in the cages approximately equal. Of the T8, T10 and T12 species produced, all conditions tried, including changing the solvent to EtOH or toluene or at reflux (THF), favor the formation of the larger cages sometimes completely excluding formation of the T8 materials. Efforts to isolate the cage compoun...

MCM-41-supported mercapto palladium(0) complex: an efficient and recyclable catalyst for the heterogeneous Stille coupling reaction

Applied Organometallic Chemistry — Tue, 01 Dec 2009 00:00:00 +0100

The Stille cross-coupling reaction of organostannanes with aryl halides was achieved in the presence of a catalytic amount of MCM-41-supported mercapto palladium(0) complex (1 mol%) in DMF[bond]H2O (9:1) under air atmosphere in good to high yields. This MCM-41-supported palladium catalyst can be reused at least 10 times without any decrease in activity. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Organotin catalysts grafted onto cross-linked polystyrene supports through polar spacers

Applied Organometallic Chemistry — Mon, 30 Nov 2009 00:00:00 +0100

The present study investigates the suitability of a HypoGel support bearing oligomeric poly(ethylene glycol) (PEG) chains to act as an insoluble carrier for grafted organotin catalysts. Through the introduction of polar spacers, an improved swelling and site accessibility in the polar media typically involved in transesterification reactions are targeted. Advanced structural investigation shows that quantitative conversion into the targeted HypoGel-supported organotin trichloride is hampered by the existence of intra- and/or intermolecular donor-acceptor O[rarr]Sn interactions caused by the presence of donor moieties in the PEG-linker. Support is provided to the proposal that the latter interactions are at the origin of the moderate catalytic performance displayed by these HypoGel-supporte...

Novel drug-based Fe(III) heterochelates: synthetic, spectroscopic, thermal and in-vitro antibacterial significance

Applied Organometallic Chemistry — Mon, 30 Nov 2009 00:00:00 +0100

A series of novel heterochelates of the type [Fe(An)(L)(H2O)2][bull]mH2O [where H2An = 4,4[prime]-(arylmethylene)bis(3-methyl-1-phenyl-4,5-dihydro-1H-pyrazol-5-ol); aryl = 4-nitrophenyl, m = 1 (H2A1); 4-chlorophenyl, m = 2 (H2A2); phenyl, m = 2 (H2A3); 4-hydroxyphenyl, m = 2 (H2A4); 4-methoxyphenyl, m = 2 (H2A5); 4-hydroxy-3-methoxyphenyl, m = 1.5 (H2A6); 2-nitrophenyl, m = 1.5 (H2A7); 3-nitrophenyl, m = 0.5 (H2A8); p-tolyl, m = 1 (H2A9) and HL = 1-cyclopropyl-6-fluoro-4-oxo-7-(piperazin-1-yl)-1,4-dihydroquinoline-3-carboxylic acid] were investigated. They were characterized by elemental analysis (FT-IR, 1H- & 13C-NMR, and electronic) spectra, magnetic measurements and thermal studies. The FAB-mass spectrum of [Fe(A3)(L)(H2O)2][bull]2H2O was determined. Magnetic moment and reflectance spec...

Design, synthesis, characterization and antibacterial properties of copper(II) complexes with chromone-derived compounds

Applied Organometallic Chemistry — Fri, 27 Nov 2009 00:00:00 +0100

A new series of six chromone-derived compounds and their Cu(II) complexes was synthesized and characterized by their physical, spectral and analytical data The elemental analysis data of the complexes agree well with the proposed composition of the compounds, which were found to be dimeric in nature with two hydrazine molecules bridging the two copper atoms through coordination. The ligands and their Cu(II) complexes were screened for their in-vitro antibacterial activity against four Gram-negative (Escherichia coli, Pseudomonas aeruginosa, Salmonella typhi, Shigella flexneri) and two Gram-positive (Bacillus subtilis, Staphylococcus aureus) bacterial strains by the agar-well diffusion method. The ligands were found to exhibit either no or low to moderate activities against one or more of t...

Synthesis and characterization of new (N-diphenylphosphino)-isopropylanilines and their complexes: crystal structure of (Ph2P[double bond] S)NH[bond]C6H4[bond]4[bond]CH(CH3)2 and catalytic activity of palladium(II) complexes in the Heck and Suzuki cross-coupling reactions

Applied Organometallic Chemistry — Thu, 26 Nov 2009 00:00:00 +0100

Three new (N-diphenylphosphino)-isopropylanilines, having isopropyl substituent at the carbon 2- (1) 4- (2) or 2,6- (3) were prepared from the aminolysis of chlorodiphenylphosphine with 2-isopropylaniline, 4-isopropylaniline or 2,6-diisopropylaniline, respectively, under anaerobic conditions. Oxidation of 1,2 and 3 with aqueous hydrogen peroxide, elemental sulfur or gray selenium gave the corresponding oxides, sulfides and selenides (Ph2P[double bond]E)NH[bond]C6H4[bond]2-CH(CH3)2, (Ph2P[double bond]E)NH[bond]C6H4[bond]4-CH(CH3)2 and (Ph2P[double bond]E)NH[bond]C6H4[bond]2,6-{CH(CH3)2}2, where E = O, S, or Se, respectively. The reaction of [M(cod)Cl2] (M = Pd, Pt; cod = 1,5-cyclooctadiene) with two equivalents of 1,2 or 3 yields the corresponding monodendate complexes [M((Ph2P)NH[bond]C6H4...

Synthesis and reactivity of some diselenasila cycles containing an annelated dicarba-closo-dodecaborane(12) unit

Applied Organometallic Chemistry — Thu, 26 Nov 2009 00:00:00 +0100

The use of 1,2-diselenolato-1,2-dicarba-closo-dodecaborane(12) dianions [1,2-(1,2-C2B10H10)Se2]2- prepared in situ as the dilithium salt may lead to irreproducible results. This is shown by the straightforward synthesis of silanes using the purified and isolated dianions, in contrast with previous less successful attempts. Thus, the reactions of the dianions with dichlorosilanes afford the five-membered diselenasila cycles containing the SiMe2 or the SiPh2 units, and with 1,2-dichloro-tetramethyldisilane the six-membered cycle containing the Si2Me4 unit. The latter was studied by X-ray diffraction, and all products were characterized by multinuclear magnetic resonance (1H, 13C, 29Si, 77Se NMR) in solution. Novel isotope effects were detected in 13C and 77Se NMR spectra. Exchange reactions ...

Enantioselective addition of diethylzinc to aldehydes catalyzed by [beta]-amino alcohols derived from (1R,2S)-norephedrine

Applied Organometallic Chemistry — Thu, 26 Nov 2009 00:00:00 +0100

[beta]-Amino alcohols derived from (1R,2S)-norephedrine were synthesized and used as ligands in the catalytic enantioselective diethylzinc addition to benzaldehydes. N-alkylated (1R,2S)-norephedrine-based derivative 3a gave the highest enantioselectivity. The effects of different parameters on the enantioselectivity of the product were investigated. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Molecular-selective adsorption property of chemically surface modified nanoporous alumina membrane by di(1-naphthyl)silanediol to anthracenes

Applied Organometallic Chemistry — Thu, 26 Nov 2009 00:00:00 +0100

Nano-porous alumina membrane (NPAM) formed by the anodic oxidation of aluminum is an attractive composite as the base material for a functional filter, because of its honeycombed ordered structure with large surface area per weight and also high shape stability. In this work, we investigated the adsorption properties of the NPAM possessing [pi]-electron systems on the surface, which were produced through chemical surface modification by di(1-naphthyl)silanediol, to aromatic compounds using anthracenes as typical aromatic compounds. The chemically surface-modified NPAM exhibited strong affinity to anthracene molecules and the affinity was observed to be weakened remarkably with the introduction of methyl and phenyl substituents to anthracene, indicating a molecular-selective adsorption prop...

A study on the heterobinuclear site of Co(salen)/TiO2[bond]SiO2 catalysts in the oxidative carbonylation of aniline

Applied Organometallic Chemistry — Thu, 26 Nov 2009 00:00:00 +0100

Titania-silica immobilized Co(salen) complexes containing the heterobinuclear site were prepared by the sol-gel method for the catalytic synthesis of methyl N-phenylcarbamate (MPC) by the oxidative carbonylation of aniline. It was found that the Ti:Si mole ratio had an important effect on the catalytic performance of Co(salen) complexes. When the Ti:Si ratio was 0.1, titania-silica supported Co(salophen) showed the best catalytic activity. Under the reaction conditions, Co(salophen)/TS-0.1, 0.5 g, aniline 11 mmol, methanol 25 ml, KI 2.2 mmol, CO:O2 9:1, total pressure 6 MPa, 150 °C, 3 h, the conversion of aniline and the selectivity of MPC were 60.7 and 88.1%, respectively. The XRD studies showed that titania was highly dispersed in the silica matrix. Co(salophen)/TS-0.1 was reused five t...

Palladium(II)-catalyzed catalytic aminocarbonylation and alkoxycarbonylation of terminal alkynes: regioselectivity controlled by the nucleophiles

Applied Organometallic Chemistry — Thu, 26 Nov 2009 00:00:00 +0100

The aminocarbonylation and alkoxycarbonylation reactions of terminal alkynes took place smoothly and efficiently using a catalyst system Pd(OAc)2-dppb-p-TsOH[bond]CH3CN[bond]CO under relatively mild experimental conditions. The catalytic system was tested and optimized using two different nucleophiles: alcohols and amines. Phenylacetylene (1a) was considered as an alkyne along with diisobutylamine (2b1) and methanol (2c1) as nucleophiles. The results showed significant differences in the conversion of 1a and in the selectivity towards the gem or trans unsaturated esters or amides with these nucleophiles. The effects of the type of palladium catalysts, the type of ligands, the amount of dppb and the solvents were carefully studied. With diisobutylamine (2b1), excellent regioselectivity towa...

Edited by Keiji Maruoka Asymmetric phase transfer catalysis Wiley-VCH, 2008, 214pp. (hardcover) ISBN 978-3-527-31842-1

Applied Organometallic Chemistry — Tue, 24 Nov 2009 00:00:00 +0100

No Abstract. (Source: Applied Organometallic Chemistry)

An efficient MnCl2-catalyzed tandem acylation-cross-coupling reaction of o-halobenzoyl chloride with diorganyl magnesium compounds

Applied Organometallic Chemistry — Fri, 06 Nov 2009 00:00:00 +0100

An efficient tandem cross-coupling reaction of o-chlorobenzoyl chloride with dialkyl and diaryl magnesium compounds in the presence of manganese (II) chloride was developed, which proceeds in good yield under mild conditions. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Synthesis, structure and biological activity of triorganotin 1H-tetrazolyl-1-acetates: cyclic hexamer and linkage coordination polymers

Applied Organometallic Chemistry — Fri, 06 Nov 2009 00:00:00 +0100

Reaction of 1H-tetrazolyl-1-acetic acid (CHN4CH2CO2H) with (R3Sn)2O or R3SnOH yields triorganotin 1H-tetrazolyl-1-acetates [CHN4CH2CO2SnR3, R = Ph (1), p-tolyl (2), cyclohexyl (3), n-Bu (4) and Et (5)]. 1H-tetrazolyl-1-acetates in these triorganotin derivatives display remarkably different coordination modes, depending on the properties of the organic substituents bonded to the tin atoms. Complex 1 displays a rare cyclohexameric structure by the assembly of the Sn[bond]N coordination bond, while complex 2 forms a linkage coordination polymer through the intermolecular Sn···N interactions. The structure of complex 3 is similar to that of complex 2, but the intermolecular Sn···N interactions are weaker in the former. However, in complex 4, the tetrazolyl nitrogen atoms do not coordinat...

Synthesis, characterization and anticancer activity of new palladacycles derived from chiral [alpha]-diimines

Applied Organometallic Chemistry — Fri, 06 Nov 2009 00:00:00 +0100

Optically pure [alpha]-diimines quantitatively obtained in solvent-free conditions starting from 2,3-butanedione and (S)-(-)-1-phenylethylamine and (S)-(-)-1-(4-methylphenyl)ethylamine, respectively, yielded the new chiral mono-Pd complexes 2a-b, which have been partly characterized by IR, 1H- and 13C-NMR spectroscopies along with MS-FAB+ spectrometry. The crystal and molecular structure for palladacycle 2a has been fully confirmed by single-crystal X-ray studies. Studies in vitro of 2a-b have displayed growth inhibition against different classes of cancer: leukemia (K-562 CML), colon cancer (HCT-15), breast cancer (MCF-7), central nervous system (U-251 Glio) and prostate cancer (PC-3) cell lines. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Synthesis of lipophilic sila derivatives of N-acetylcysteineamide, a cell permeating thiol

Applied Organometallic Chemistry — Fri, 06 Nov 2009 00:00:00 +0100

N-acetyl-L-cysteine (L-NAC) is a potent antioxidant that can reduce levels of reactive oxygen species. N-acetyl-cysteine-amide, the amide form of L-NAC, has recently been reported to be more lipophilic and permeable through cell membranes than NAC, and to be able to traverse the blood-brain barrier. In this communication we report the synthesis and characterization of highly lipophilic sila-amide derivatives of L-NAC that may show enhanced cell penetration and bioavailability. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Preparation and cytotoxic properties of goethite-based nanoparticles covered with decyldimethyl(dimethylaminoethoxy) silane methiodide

Applied Organometallic Chemistry — Fri, 06 Nov 2009 00:00:00 +0100

The present work describes the synthesis, physico-chemical and biological properties of the first water-soluble goethite nanoparticles covered with biologically active components: oleic acid and cytotoxic decyldimethyl(dimethylaminoethoxy)silane methiodide. The structure of initial goethite nanoparticles synthesized was proved by XRD analysis and the rough estimation of nanoparticles core size gave the value of 8 nm. The size of colloidal water-soluble nanoparticles, determined by dynamic light scattering, was within 19-35 nm. Magnetic properties and cytotoxicity (against HT-1080 and MG-22A tumor cell lines) of the nanoparticles obtained were investigated. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Highly efficient catalytic system for electrophilic amination of arylzinc reagents

Applied Organometallic Chemistry — Fri, 06 Nov 2009 00:00:00 +0100

The effect of catalyst on the yield of amine in the amination of three classes of arylzinc reagents with acetone oxime O-tosylate was investigated. Since they allowed the preparation of arylamines in excellent yields in the presence of a minimum amount of copper (I) or copper (II) compounds, the catalytic systems using copper (I) or copper (II) combined with a P-, N- or S-donor ligand were revealed to be the best catalysts for the electrophilic amination of arylzinc reagents with acetone oxime O-tosylate in the presence of DMPU. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Homo- and heteropolynuclear copper(II) complexes containing a new diimine-dioxime ligand and 1,10-phenanthroline: synthesis, characterization, solvent-extraction studies, catalase-like functions and DNA cleavage abilities

Applied Organometallic Chemistry — Fri, 23 Oct 2009 23:00:00 +0100

A series of homo-, heterodinuclear and homotrinuclear copper(II) complexes containing a new Schiff base ligand and 1,10-phenanthroline were synthesized. Based on results of elemental analyses, FTIR, 1H- and 13C-NMR spectra, conductivity measurements and magnetic susceptibility measurements, the complexes had general compositions {[Cu(L)(H2O)M(phen)2](ClO4)2 [M = Cu(II), Mn(II), Co(II)]} and {[Cu3(L)2(H2O)2](ClO4)2}. The metal:L:phen ratio is 2:1:2 for the dinuclear copper(II) complexes and the metal:L ratio was 3:2 for the trinuclear copper(II) complex. The liquid-liquid extraction of various transition metal cations [Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pb(II), Cd(II), Hg(II)] from the aqueous phase to the organic phase was carried out using the diimine-dioxime ligand. It was concluded...

Preparation and properties of polyhedral oligomeric silsesquioxane-polysiloxane copolymers

Applied Organometallic Chemistry — Wed, 21 Oct 2009 23:00:00 +0100

All siloxane-type siloxane-polyhedral oligomeric silsesquioxane [(HSiO3/2)8, T8H] copolymers were synthesized by the dehydrogenative condensation of T8H with diphenylsilanediol, tetraphenyldisiloxane-1,3-diol or silanol-terminated polydimethylsiloxanes in the presence of diethylhydroxylamine followed by trimethylsilylation. Coating films were prepared by spin-coating of the coating solutions prepared from the dehydrogenative condensation products. The hardness of the coating films was evaluated by a pencil hardness test and was found to increase up to 6H with increases in the curing temperature. Silica gels were prepared by concentrating the coating solution following by pyrolysis. These silica gels showed a specific surface area 449 m2/g at 650 °C corresponding to the formation of a sili...

Synthesis, X-ray powder structure analysis and biological properties of a mononuclear Cu(II) complex of N-2-hydroxyhippuric acid

Applied Organometallic Chemistry — Tue, 20 Oct 2009 23:00:00 +0100

A mononuclear copper (II) complex of N-2-hydroxyhippuric acid (2HHA), [Cu(HA)(H2O)2], has been synthesized and characterized by spectroscopic and X-ray powder diffraction studies. Crystal structure of [Cu(HA)(H2O)2] reveals a distorted square-pyramidal geometry around the metal center. The crystal packing in the complex exhibits a three-dimensional framework formed by intermolecular O[bond]; H···O and C[bond]H···O hydrogen bonds. Toxicity and antitumor properties of the complex have been studied in vivo. The complex, capable of depleting glutathione (GSH) at nontoxic doses, may be utilized to sensitize drug-resistant cells where resistance is due to an elevated level of GSH. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Polyhedral oligomeric silsesquioxane-bound iminofullerene

Applied Organometallic Chemistry — Tue, 20 Oct 2009 23:00:00 +0100

Polyhedral oligomeric silsesquioxane (POSS) cages containing an iminofullerene species are reported herein. Monosubstituted benzyl chloride POSS was synthesized, and subsequently reacted with sodium azide to form mono benzyl azide POSS. The azide was subsequently reacted with C60 in anhydrous, degassed toluene to yield the desired POSS iminofullerene compound. The prepared compounds were characterized by multinuclear NMR, electrospray mass spectrometry, elemental analysis, UV-vis, fluorescence and optical power limiting measurements. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Accelerated Heck reaction using ortho-palladated complex with controlled microwave heating

Applied Organometallic Chemistry — Tue, 20 Oct 2009 23:00:00 +0100

Palladium-catalyzed Heck couplings utilizing [Pd{C6H2(CH2CH2NH2)-(OMe)2,3,4} (µ-Br)]2 palladacycle catalyst and microwave irradiation lead to formation of different coupling products. This complex is an active and efficient catalyst for the Heck reaction of aryl iodides, bromides and even less reactive chlorides. The cross-coupled products were produced in excellent yields. The reaction time was reduced from hours to minutes and full conversion was achieved under microwave irradiation. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Asymmetric 1,4-conjugation addition of diethylzinc to cyclic enones catalyzed by a self-assembled copper complex

Applied Organometallic Chemistry — Wed, 14 Oct 2009 23:00:00 +0100

A new self-assembled catalyst system based on copper complex was developed for the 1,4-conjugation addition of diethyl zinc to cyclic enones. The self-assembled catalyst was readily prepared from (R)-[1,1[prime]]binaphthalenyl-2,2[prime]-diamine (1a), (L)-tryptophan (3f) and copper(I) chloride (CuCl). Several enones were found to be suitable substrates in the presence of the self-assembled copper catalyst [10 mol% (R)-1a, 10 mol% (L)-3f and 10 mol% CuCl] under optimized conditions. The desired products were afforded with high isolated yields (up to 98%) and moderate to good enantioselectivities (up to 80% ee) in mild conditions (at 0 °C). Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Edited by Armin Börner phosphorus ligands in asymmetric catalysis: synthesis and applications Wiley-VCH, 2008, 1546 pp. (hardcover) ISBN 978-3-527-31746-2

Applied Organometallic Chemistry — Wed, 14 Oct 2009 23:00:00 +0100

No Abstract. (Source: Applied Organometallic Chemistry)

Palladium supported on polyether-functionalized mesoporous silica. Synthesis and application as catalyst for Heck coupling reaction

Applied Organometallic Chemistry — Wed, 14 Oct 2009 23:00:00 +0100

A new catalytic system based on Pd supported on polyether-functionalized mesoporous silica was prepared. This material was obtained by co-hydrolysis and polycondensation of tetraethylorthosilicate and a bis-silylated triblock copolymer P123 (Mw = 5800) followed by the decomposition of Pd(OAc)2 salt. We have shown that this material can be applied as powerful heterogeneous catalyst for the Heck coupling reaction. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Synthesis of star-shaped molecules with pyrene-containing [pi]-conjugated units linked by an organosilicon core

Applied Organometallic Chemistry — Tue, 13 Oct 2009 23:00:00 +0100

Star-shaped molecules with pyrene-containing [pi]-conjugated units linked by an organosilicon core (Py3Si and Py3C) were prepared and their applications to thin-film transistors (TFTs) and photovoltaic cells were studied. Bottom-contact type TFTs with spin-coated films of the star-shaped compounds as the active layers were prepared and the field-effect mobility (µFET) and Ion/Ioff ratios were determined to be approximately 10-5 cm2 V-1 s-1 and 104, respectively. Photovoltaic properties of Py3Si and Py3C were studied in the cells, ITO-PEDOT-PSS-Py3Si or Py3C-PCBM-LiF-Al. Although the power conversion efficiency (PCE) of the cells was only about 0.04%, they showed high open circuit voltages (Voc) of 0.8-0.9 V, indicating the high potential of this type of compound as a host material. Copyri...

Accelerated ceramization of polymethylsilsesquioxane by aluminum- based filler reductant

Applied Organometallic Chemistry — Tue, 13 Oct 2009 23:00:00 +0100

Polymethylsilsesquioxane (PMSQ), compounded with particles of Al2O3 (22-47 nm), micro size aluminum (30 µm) or nano size aluminum (50 nm) with a starting Al:Si molar ratio of 1.0, was prepared in a thick sheet form and pyrolyzed at various temperatures up to 1673 K to investigate the filler effect on the ceramization. By adjusting the concentrations of PMSQ, filler and cross-linking agent in ethanol, self-standing ceramic sheets were obtained after pyrolysis without fragmentation. The phases formed in each sheet during pyrolysis were identified by using X-ray diffraction patterns. The resulting micro structures were characterized by the Archimedes method, SEM observation and electron micro probe analysis. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Iron-catalyzed efficient three-component allylation of imine in aqueous media

Applied Organometallic Chemistry — Thu, 08 Oct 2009 23:00:00 +0100

Iron trichloride hexahydrate has proved to be a very effective catalyst for the three-component condensation of aromatic aldehydes, amines and allyltributylstannane, which produces high yields of homoallylic amines in water in the presence of surfactant SDS. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

A convenient synthesis of nanocrystalline chalcopyrite, CuFeS2 using single-source precursors

Applied Organometallic Chemistry — Thu, 08 Oct 2009 23:00:00 +0100

Nanocrystalline chalcopyrite (CuFeS2) have been synthesized using single-source precursors, CuL2 and Cu(LH)2Cl2 (where LH = monoacetylferrocene thiosemicarbazone) by pyrolysis and solvothermal decomposition methods. The nanocrystals were characterized by UV-visible spectroscopy, X-ray powder diffraction, transmission electron microscopy and energy dispersive X-ray analysis. The magnetic character was determined by the hysteresis loop. CuFeS2 nanocrystallites prepared by the pyrolysis of CuL2 and Cu(LH)2Cl2 have a cubic phase and rod-like morphology with diameters of about 18 and 15 nm, respectively, and lengths of about 195-390 and 100-145 nm, respectively. However, CuFeS2 nanoparticles obtained by solvothermal route from CuL2 and Cu(LH)2Cl2, which are capped with ethylene glycol, possess ...

New route to synthesis of PVP-stabilized palladium(0) nanoclusters and their enhanced catalytic activity in Heck and Suzuki cross-coupling reactions

Applied Organometallic Chemistry — Wed, 07 Oct 2009 23:00:00 +0100

Herein we report a new method for the synthesis and characterization of PVP-stabilized palladium(0) nanoclusters and their enhanced catalytic activity in Suzuki coupling and Heck reactions of aryl bromides with phenylboronic acid and styrene, respectively, under mild conditions. The PVP-stabilized palladium(0) nanoclusters with a particle size of 4.5 ± 1.1 nm were prepared using a new method: refluxing a mixture of potassium tetrachloropalladate(II) and PVP in methanol at 80 °C for 1 h followed by reduction with sodium borohydride. Palladium(0) nanoclusters prepared in this way were stable in solution for weeks, could be isolated as solid materials and were characterized by TEM, XPS, UV-vis, and XRD techniques. The PVP-stabilized palladium(0) nanoclusters were active catalysts in Heck an...

JOAN RIBAS GISPERT Coordination chemistry Wiley-VCH, 2008, 600 pp. (paperback) ISBN-10 3-527-31802-X ISBN-13 978-3-527-31802-5

Applied Organometallic Chemistry — Wed, 30 Sep 2009 23:00:00 +0100

No Abstract. (Source: Applied Organometallic Chemistry)

Synthesis, characterization and hydroformylation activity of 7-azaindolate-bridged dinuclear rhodium(I)phosphines with pendant polar-groups

Applied Organometallic Chemistry — Tue, 29 Sep 2009 23:00:00 +0100

New dinuclear Rh(I)-Phosphines of the types [Rh(µ-azi)(CO)(L)]2 (1,3-7) and [Rh(µ-azi)(L)]2 (8) with pendant polar groups, and a chealated mononuclear compound [Rh(azi-H)(CO)(L)] (2) (where azi = 7-azaindolate, L = polar phosphine) were isolated from the reaction of [Rh(µ-Cl)(CO)2]2 with 7-azaindolate followed by some polar mono- and bis-phosphines (L1-L8). A relationship between [Delta][delta]31P-NMR and [nu](CO) values was considered to define the impact of polar-groups on [sigma]-donor properties of the phosphines. These compounds were evaluated as catalyst precursors in the hydroformylation of 1-hexene and 1-dodecene both in mono- and biphasic aqueous organic systems. While the biphasic hydroformylations (water + toluene) gave exclusively the aldehydes, the monophasic one (aqueous e...

Silane reduction of onium salts

Applied Organometallic Chemistry — Tue, 29 Sep 2009 23:00:00 +0100

Novel redox initiators for cationic polymerizations were developed consisting of an onium salt together with a Si[bond]H functional silane or siloxane. The reduction of the onium salt by the silane is catalyzed by noble metal complexes or certain transition metal compounds and takes place spontaneously at room temperature. The redox reaction of the onium salt with the silane results in the liberation of a strong Brønsted acid that can be subsequently used to initiate cationic polymerizations. Typical onium salts that have been employed in these redox initiator systems are diaryliodonium salts, triarylsulfonium salts and S,S-dialkyl-S-phenacylsulfonium salts. Studies of the effects of variations in the structures of the onium salt, the silane and the type of noble metal catalyst were carri...

Synthesis of 4-substituted styrene compounds via palladium catalyzed Suzuki-Miyaura reaction using bidentate Schiff base ligands

Applied Organometallic Chemistry — Wed, 16 Sep 2009 23:00:00 +0100

Air-stable symmetric Schiff base have been synthesized and proved to be efficient ligands for Suzuki-Miyaura reaction between aryl bromides and arylboronic acids using PdCl2(CH3CN)2 as palladium source under aerobic conditions. The coupling reaction proceeded smoothly using N,N-bis(anthracen-9-ylmethylene)benzene-1,2-diamine (L7) as ligand to provide 4-substituted styrene compounds in good yields. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Synthesis and cytotoxic activity of new 2-[(3-aminopropyl)dimethylsilyl]-5-triethylsilylfurans

Applied Organometallic Chemistry — Tue, 15 Sep 2009 23:00:00 +0100

Highly cytotoxic 3-aminopropyl derivatives of 5-triethylsilyl-2-dimethylsilylfuran (LC501-3 µg ml-1) have been prepared by hydrosilylation of heterocyclic N-allylamines with corresponding hydrosilane in the presence of Speier's catalyst. The influence of the amine structure on the cytotoxicity has been investigated. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Biphasic oligomerization of ethylene with nickel complexes immobilized in organochloroaluminate ionic liquids

Applied Organometallic Chemistry — Tue, 15 Sep 2009 23:00:00 +0100

Ethylene was selectively oligomerized by nickel complexes such as (PPh3)2NiBr2 and (PPh3)2NiCl2 immobilized in chloroaluminate ionic liquid in biphasic catalytic reactions. The influence of reaction parameters such as reaction media, reaction temperature and Et2AlCl:Ni molar ratio was also evaluated. Turnover frequency up to 24000 mol C2H4/(mol Ni h) was achieved under mild reaction conditions (0.5 atm and 40 °C). GC-MS analyses showed that the obtained oligomers completely consist of C4 and C6. The olefinic products can be easily separated from the catalytic ionic liquid phase by simple decantation, and the nickel catalyst can be reused without a significant decrease in turnover frequency and change of the distribution of the olefinic products. Copyright © 2009 John Wiley & Sons, Ltd. (...

Synthesis and characterization of transition metal complexes of thiophene-2-methylamine: X-ray crystal structure of palladium (II) and platinum (II) complexes and use of palladium(II) complexes as pre-catalyst in Heck and Suzuki cross-coupling reactions

Applied Organometallic Chemistry — Tue, 15 Sep 2009 23:00:00 +0100

The reactions of thiophene-2-(N-diphenylphosphino)methylamine, Ph2PNHCH2-C4H3S, 1 and thiophene-2-[N,N-bis(diphenylphosphino)methylamine], (Ph2P)2NCH2-C4H3S, 2, with MCl2(cod) (M = Pd, Pt; cod = 1,5-cyclooctadiene) or [Cu(CH3CN)4]PF6 yields the new complexes [M(Ph2PNHCH2-C4H3S)2Cl2], M = Pd 1a, Pt 1b, [Cu(Ph2PNHCH2-C4H3S)4]PF6, 1c, and [M(Ph2P)2NCH2-C4H3S)Cl2], M = Pd 2a, Pt 2b, {Cu[(Ph2P)2NCH2-C4H3S]2}PF6, 2c, respectively. The new compounds were isolated as analytically pure crystalline solids and characterized by 31P-, 13C-, 1H-NMR and IR spectroscopy and elemental analysis. Furthermore, the solid-state molecular structures of representative palladium and platinum complexes of bis(phosphine)amine, 2a and 2b, respectively, were determined using single crystal X-ray diffraction analysis. ...

Synthesis, characterization and DNA binding and photocleavage studies of [Ru(bpy)2BDPPZ]2+, [Ru(dmb)2BDPPZ]2+ and [Ru(phen)2BDPPZ]2+ complexes and their antimicrobial activity

Applied Organometallic Chemistry — Sun, 23 Aug 2009 23:00:00 +0100

Polypyridyl ligand 9a,13a-dihydro-4,5,9,14-tetraaza-benzo[b]triphenylene-11-yl)-phenyl-methanone (BDPPZ) and its complexes [Ru(bpy)2BDPPZ]2+, [Ru(dmb)2BDPPZ]2+ and [Ru(phen)2BDPPZ]2+ (where bpy = 2,2[prime]-bipyridine, dmb = 4,4[prime]-dimethyl-2,2[prime]-bipyridine, phen = 1,10-phenanthroline) have been synthesized and characterized by elemental analysis, IR, UV-vis, 1H-NMR, 13C-NMR and mass spectra. The DNA-binding properties of the complexes were investigated by absorption, emission, melting temperature and viscosity measurements. Experimental results indicate that the three complexes can intercalate into DNA base pairs. Photo activated cleavage of pBR-322 DNA by the three complexes was also studied. Further, all three Ru(II) complexes synthesized were screened for their antimicrobial a...

Synthesis, structure and muscarinic agonist activity of substituted N-(silatran-1-ylmethyl)acetamides

Applied Organometallic Chemistry — Fri, 21 Aug 2009 23:00:00 +0100

Substituted N-(silatran-1-ylmethyl)acetamides, N-methyl-N-[1-(3[prime],7[prime],10[prime]-trimethylsilatran-1-yl)methyl]acetamide (2a) and N-(2-hydroxyethyl)-N-[1-(3[prime],7[prime],10[prime]-trimethylsilatran-1-yl)methyl]acetamide (2b) were prepared by the reactions of triisopropanolamine with N-methyl-N-(trimethoxysilylmethyl)acetamide (1a) and 2,2-dimethoxy-4-acetyl-1-oxa-4-aza-2-silacyclohexane (1b), respectively. According to X-ray data, the structures of the silatrane moieties are superpositions of unsymmetrical and symmetrical stereoisomers. The O [rarr] Si coordination between the central atom and exocyclic substituent is absent in both compounds. Silatranes 2a and 2b are partial muscarinic agonists which demonstrate submaximal effect and mimic the effect of acetylcholine by bindin...

Synthesis, structural characterization, biological activity and thermal study of tri- and diorganotin(IV) complexes of Schiff base derived from 2-aminomethylbenzimidazole

Applied Organometallic Chemistry — Tue, 18 Aug 2009 23:00:00 +0100

This report deals with the synthesis and structural features of tri- and diorganotin(IV) complexes of the general formulae, RnSn(L)m [n = 3, m = 1, R = Me, n-Bu and Ph; n = 2, m = 2, R = Me, n-Bu, n-Oct and Ph; HL = Schiff base derived from the condensation of 2-aminomethylbenzimidazole (ambmz) and salicylaldehyde (abbreviated as HL or Hsal-ambmz)]. The newly synthesized complexes were characterized by elemental analysis, molar conductance, electronic, infrared, far-infrared, 1H NMR, 13C NMR, 119Sn NMR and 119Sn Mössbauer spectral studies. Thermal studies of all of the synthesized complexes were also carried out using thermogravimetry-differential thermal analysis-derivative thermogravimetric (TG-DTA-DTG) techniques. The residues thus obtained were characterized by infrared and powder X-r...

Luminescent organo-polysiloxanes containing complexed lanthanide ions

Applied Organometallic Chemistry — Mon, 17 Aug 2009 23:00:00 +0100

In this study, a type of polysiloxane with the ester as the functional side group was prepared via a hydrosilylation reaction. The functionalized polysiloxane was then allowed to complex with Tb3+ and Eu3+ ions. Fourier transform infrared, ultraviolet absorption spectra and 1H-NMR, 13C-NMR and 29Si-NMR spectra were used to confirm the modification. Differential scanning calorimetry and thermal gravity analysis were used to study the polysiloxane's thermal properties. The complexes' luminescence spectra were recorded, and narrow-width green and red emissions were achieved. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Rapid, highly efficient and chemoselective trimethylsilylation of alcohols and phenols with hexamethyldisilazane (HMDS) catalyzed by reusable electron-deficient tin(IV)porphyrin

Applied Organometallic Chemistry — Mon, 17 Aug 2009 23:00:00 +0100

In this paper, rapid and highly efficient trimethylsilylation of alcohols and phenols with hexamethyldisilazane (HMDS) in the presence of catalytic amounts of high-valent [SnIV(TPP)(OTf)2] is reported. This catalytic system catalyzes trimethylsilylation of primary, secondary and tertiary alcohols as well as phenols, and the corresponding TMS-ethers were obtained in high yields and short reaction times at room temperature. It is noteworthy that this method can be used for chemoselective silylation of primary alcohols in the presence of secondary and tertiary alcohols and phenols. The catalyst was reused several times without loss of its catalytic activity. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Synthesis, structural characterization and electrochemical recognition of metal ions of two new ferrocenylhydrazone-based receptors

Applied Organometallic Chemistry — Fri, 14 Aug 2009 23:00:00 +0100

Two new ferrocenylhydrazone-based receptors FcL1 and FcL2 were prepared and the X-ray crystal structure of FcL1 was described. The electrochemical studies reveal that the receptor FcL1 is responsive to Hg2+ and Cr3+, whereas, receptor FcL2 only responsive to Hg2+. The maximum electrochemical shift of FcL1 for Cr3+ is about 56 mV. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Edited by K. Morokuma and D. Musaev Computational modeling for homogeneous and enzymatic catalysis: a knowledge-base for designing efficient catalysts Wiley-VCH, 2008, 398 pp. (hardover) ISBN 978-3-527-31843-8

Applied Organometallic Chemistry — Mon, 10 Aug 2009 23:00:00 +0100

No Abstract. (Source: Applied Organometallic Chemistry)

The conversion of an organometallic compound into an intercalated thin-layer amorphous structure

Applied Organometallic Chemistry — Wed, 05 Aug 2009 23:00:00 +0100

A thin alumina-hydrotalcite (Al-HT) film was fabricated from the synthesized boehmite and HT sol samples. The sols were a Newtonian fluid within 12 h of the sol synthesis and pseudo-plastic flow thereon. Co-precipitated HT demonstrated poorly crystallized periclase and spinel structures and apparent doublet peak of hydrotalcite at 2[thetas] = 39-44°, indicative of a disordered structure. The heated Al-HT sample demonstrated highly amorphous structure with single hydrotalcite peak but barely observed [gamma]-alumina and [gamma]-boehmite phases. The exfoliation of the spinel, gibbsite and periclase in the Al-HT was caused by the intercalation of boehmite into the HT layers that impeded the formation of the oxides phases. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometal...

Synthesis of 2,4,6-trisubstituted naphthalenes via novel copper-promoted tandem coupling and intramolecular cyclization

Applied Organometallic Chemistry — Fri, 24 Jul 2009 23:00:00 +0100

An unprecedented copper-promoted tandem coupling and intramolecular cyclization reaction is disclosed. This strategy offers a simple and promising method for accessing 2,4,6-trisubstituted naphthalenes. A reaction mechanism involving initial formation of diynes followed by a 6-exo-dig cyclization and subsequent rearrangement is proposed. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Edited by László Kollár Modern carbonylation methods Wiley-VCH, 2008, 383 pp. (hardcover) ISBN 978-3-527-31896-4

Applied Organometallic Chemistry — Thu, 23 Jul 2009 23:00:00 +0100

No Abstract. (Source: Applied Organometallic Chemistry)

Betti base-derived tetradentate ligand: synthesis and application in copper-catalyzed N-arylation of imidazoles

Applied Organometallic Chemistry — Thu, 16 Jul 2009 23:00:00 +0100

Betti base-derived tetradentate ligand 2 has been successfully designed and synthesized through the condensation of Betti base with glyoxal. Its application in N-arylation of imidazoles has been investigated which opens a new field for application of Betti base derivatives in organic transformation. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Antibacterial, spectral and thermal aspects of drug based-Cu(II) mixed ligand complexes

Applied Organometallic Chemistry — Thu, 16 Jul 2009 23:00:00 +0100

The antibiotic agent clioquinol is well known for its drug design and coordinating ability towards metal ions. Copper(II) mixed-ligand complexes of clioquinol with various uninegative bidentate ligands were prepared. The structure of the synthesized complexes was characterized using elemental analyses, infrared spectra, 1H-NMR spectra, electronic spectra, magnetic measurements, FAB mass spectrum and thermo gravimetric analyses. The kinetic parameters such as order of reaction (n) and the energy of activation (Ea) are reported using the Freeman-Carroll method. The pre-exponential factor (A), the activation entropy ([Delta]S#), the activation enthalpy ([Delta]H#) and the free energy of activation ([Delta]G#) were calculated. Complexes were also screened for their in vitro antibacterial activ...

Water as green oxidant: a highly selective conversion of organosilanes to silanols with water

Applied Organometallic Chemistry — Thu, 16 Jul 2009 23:00:00 +0100

Selective hydrolytic oxidation of organohydrosilanes was achieved with water in the presence of Pt-nanoparticle catalyst. The selectivity of the process was established by NMR analysis. In addition, various Pt-based catalysts were screened to compare the activity and selectivity with Pt-nanoparticles catalysis. The method was equally applicable to hydrosilanes bearing unsaturated functional groups, which led to corresponding silanols under mild reaction conditions without formation of any side products. Pt-nanoparticle catalysis was studied in details using UV-vis, TEM and mercury poisoning experiments during the transformation. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Direct coupling reaction between alcohols and allyltrimethylsilane catalyzed by phosphomolybdic acid

Applied Organometallic Chemistry — Wed, 15 Jul 2009 23:00:00 +0100

Phosphomolybdic acid (PMA) is a simple and efficient catalyst for direct coupling reaction of alcohols with allyltrimethylsilane. Direct nucleophilic allylation of alcohol with allyltrimethylsilane proceeds in considerably good yield in the presence of catalytic amount of (0.5 mol %) PMA at room temperature. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Synthesis and characterization of some novel silicon esters and their application as lubricant base stock solution

Applied Organometallic Chemistry — Mon, 13 Jul 2009 23:00:00 +0100

A series of functional organosilanes and their esters were synthesized by the hydrosilylation reaction of Si[bond]H group-bearing organosilicon derivatives with maleic anhydride using Speier's catalyst and their esterification with long-chain alcohols in the presence of stannous oxide. These products have been characterized using elemental analysis, FT-IR, 1H, 13C and 29Si NMR. Viscosity, density, pour point, flash point and tribological properties of these compounds have also been evaluated. These esters have a pour point of (Source: Applied Organometallic Chemistry)

By William R.Cullen Is arsenic an aphrodisiac? The sociochemistry of an element Royal Society of Chemistry, 2008, 412 pp. ISBN 0854043632, 9780854043637

Applied Organometallic Chemistry — Thu, 09 Jul 2009 23:00:00 +0100

No Abstract. (Source: Applied Organometallic Chemistry)

Synthetic hydrotalcites from different routes and their application as catalysts and gas adsorbents: a review

Applied Organometallic Chemistry — Tue, 07 Jul 2009 23:00:00 +0100

In this paper, widely accepted methods of hydrotalcite preparation such as co-precipitation, urea hydrolysis, hydrothermal, sol-gel, microwave irradiation, steam activation and solvothermal have been selected and reviewed. Our review indicates that the nature of the divalent cations, the synthesis method, the calcination temperature and the nature of the interlayer species are determinant factors in shaping the surface properties of the layered double hydoxides. The basic strength of the surface base site and structural changes produced in the mixed oxides can be adjusted conveniently by varying the Al content during the synthesis. The combination of sol-gel with microwave irradiation during the gelling and crystallization steps has also been found to increase the surface area of the hydro...

Organotin(IV) tryptophanylglycinates: potential non-steroidal antiinflammatory agents; crystal structure of dibutyltin(IV) tryptophanylglycinate

Applied Organometallic Chemistry — Mon, 06 Jul 2009 23:00:00 +0100

Diorganotin(IV) derivatives of tryptophanylglycine (H2Trp-Gly) with general formula R2Sn(Trp-Gly), where R = Me, n-Bu, Ph and n-Oct, and triorganotin(IV) derivatives R[prime]3 Sn(HTrp-Gly) where R[prime] = Me, n-Bu and Ph, have been synthesized and structurally characterized in the 'solid state as well as in solution on the basis of various spectroscopic techniques, viz. FT-IR, multinuclear 1H, 13C and 119Sn NMR, 119Sn Mössbauer and single crystal X-ray diffraction. These investigations suggest that tryptophanylglycine in R2Sn(Trp-Gly) acts as dianionic tridentate coordinating through carboxylate oxygen [[bond]C(O)O-], amino nitrogen ([bond]NH2) and N-peptide, while in the case of R[prime]3 Sn(HTrp-Gly), the ligand acts as monoanionic bidentate coordinating through [bond]C(O)O- and [bond]...

Synthesis, characterization and oxygen-sensing properties of a novel luminescent Cu(I) complex

Applied Organometallic Chemistry — Fri, 26 Jun 2009 23:00:00 +0100

A novel luminescent copper(I) complex with formula [Cu(PPh3)2(PIP)]BF4 (PPh3 = triphenyl phosphine, PIP = 2-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline) has been synthesized and characterized by 1H NMR, IR, elemental analysis and X-ray crystal structure analysis. In solid state, it displays broad band emission upon excitation at [lambda] = 420 nm with the emission maximum locates at 551 nm. Its excited-state lifetime is in the microsecond time scale (3.02 µs); as a result, its emission intensity is sensitive to oxygen concentration and shows oxygen-sensing properties after being encapsulated into mesoporous silica MCM-41. For the system with 60 mg/g loading level, a sensitivity (I0/I) of 4.35, a fluorescence quenching time (tQ) of 5 s and a recovery time (tR) of 36 s were achieved. Even ...

Mono-, bis- and tris-piperidine fused imidazolinium salts: their in situ catalytic applications for C[bond]C bond formation in aqueous solutions

Applied Organometallic Chemistry — Wed, 24 Jun 2009 23:00:00 +0100

The 1,5,6,7,8,8a-hexahydroimidazo[1,5-a]pyridine, 3, was quaternized with 2-(bromomethyl-1,3,5-trimethylbenzene, 1,4-bis(bromomethyl)-2,3,5,6-tetramethylbenzene, 2,4-bis(bromomethyl)-1,3,5-trimethylbenzene, 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene and 1,3,5-tris(bromomethyl)-2,4,6-triethylbenzene to obtain mono-, bis- and tris-imidazolinium salts (4-7) which were characterized by elemental analysis and NMR spectroscopy. In order to understand the effects of these changes on the N-substituent and how they translate to catalytic activity, these new salts (4-7) with Pd(OAc)2 were applied as in situ catalysts for Suzuki-Miyaura and Heck-Mirozoki cross-coupling reactions of aryl chlorides and aryl bromides, respectively. The tris-imidazolinium salts (7) were found to be more efficient tha...

Edited by Antonio Violante, Pan Ming Huang, Geoffrey M. Gadd Biophysico-chemical processes of heavy metals and metalloids in soil environments Wiley, 2008, 658 pp. (hardcover) ISBN 978-0-471-73778-0

Applied Organometallic Chemistry — Tue, 23 Jun 2009 23:00:00 +0100

No Abstract. (Source: Applied Organometallic Chemistry)

BY DIETER REHDER Bioinorganic vanadium chemistry John Wiley & Sons/Wiley-Blackwell, 2008, 224 pp. (paperback), (hardcover) ISBN 978-0-470-06516-7, 978-0-470-06509-9

Applied Organometallic Chemistry — Mon, 22 Jun 2009 23:00:00 +0100

No Abstract. (Source: Applied Organometallic Chemistry)

EDITED BY PETR ST[Ecaron]PNI[Ccaron]KA Ferrocenes: ligands, materials and biomolecules John Wiley & Sons/Wiley-Blackwell, 2008, 670 pp. ISBN 978-0-470-03585-6 (hardcover)

Applied Organometallic Chemistry — Mon, 22 Jun 2009 23:00:00 +0100

No Abstract. (Source: Applied Organometallic Chemistry)

Aminophosphines: their chemistry and role as ligands and synthons

Applied Organometallic Chemistry — Sun, 21 Jun 2009 23:00:00 +0100

In recent years, research in organophosphorus chemistry has mainly focused in designing newer and better phosphorus ligands for synthesizing novel metal complexes with improved catalytic activities. Aminophosphines [tricoordinate phosphorus(III)-nitrogen systems] are considered as versatile compounds owing to the presence of nitrogen centres which, in principle, can influence additional reactivity features. They are quite sensitive to air and moisture due to the presence of polar P[bond]N bond(s). In spite of this, research in aminophosphine chemistry is gaining momentum day-by-day and this is due mainly to one reason: their rich behaviour as ligands in metal complex chemistry and subsequently in catalysis. Their role as synthons in inorganic heterocyclic chemistry has also helped produce ...

Novel types of boronated chlorin e6 conjugates via 'click chemistry'

Applied Organometallic Chemistry — Sun, 21 Jun 2009 23:00:00 +0100

Conjugates of chlorin e6 with closo-dodecaborate and cobalt bis(dicarbollide) anions were synthesized for the first time in high yields using the advanced 'click' methodology. In vitro study on A549 human lung adenocarcinoma cells revealed that the synthesized boronated conjugates are able to penetrate and accumulate in cancer cells, but their intracellular concentration is not sufficient for effective photodynamic and boron neutron capture therapy of cancer. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Application of carbon arc-generated Mo- and W-based catalyst systems to the ROMP of norbornene

Applied Organometallic Chemistry — Wed, 17 Jun 2009 23:00:00 +0100

This study focuses on the application of the carbon arc-generated molybdenum- and tungsten-based catalyst systems, MoCl5[bond]C and WCl6[bond]C, to effect ring-opening metathesis polymerization (ROMP) of bicyclo[2.2.1]hept-2-ene (norbornene). The results are compared with those previously obtained by the electrochemically generated MoCl5[bond][emacr][bond]Al[bond]CH2Cl2 and WCl6[bond][emacr][bond]Al[bond]CH2Cl2 systems. The polymer products are characterized using 1H and 13C NMR, gel permeation chromatography, differential scanning calorimetry and thermo gravimetric analysis. According to NMR spectra analyses, the molybdenum-based catalyst system produced polynorbornene with ca 48% cis structure whereas tungsten system produced ca 56% cis structure polynorbornene and in both cases the poly...

2-Pyridylquinoxaline derivatives as N,N-ligands for palladium-catalyzed Suzuki-Miyaura reaction

Applied Organometallic Chemistry — Tue, 16 Jun 2009 23:00:00 +0100

The Suzuki-Miyaura reaction of aryl bromides with benzeneboronic acid catalyzed by bis(chloro)(2-pyridylquinoxaline)palladium(II) was investigated. The scope of the bis(chloro)(2-pyridylquinoxaline)palladium(II) was determined in toluene at 80 °C using KOH as base. Using a 0.1% molar ratio of bis(chloro)(2-pyridylquinoxaline)palladium(II) C1 as a catalyst, aryl bromides reacted with benzeneboronic acid to afford diaryl derivatives in excellent yield. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Synthesis, characterization and biological properties of sulfonamide-derived compounds and their transition metal complexes

Applied Organometallic Chemistry — Sat, 30 May 2009 04:00:00 +0100

Sulfonamide-derived compounds and their first row d-transition metal chelates [cobalt(II), copper(II), nickel(II) and zinc(II)] have been synthesized and characterized. The nature of bonding and structure of all the synthesized compounds have been proposed from magnetic susceptibility and conductivity measurements, IR, 1H and 13C NMR, electron spectra, mass spectrometry and CHN analysis data. The structure of ligand, 4-{[(E)-(5-chloro-2-hydroxyphenyl) methylidene] amino}-N-(4,6-dimethyl pyrimidin-2-yl) benzene sulfonamide has also been determined by X-ray diffraction method. An octahedral geometry has been suggested for all the complexes. The ligands and metal complexes have been screened for their in vitro antibacterial, antifungal and cytotoxic activity. The results of these studies reve...

Metal-based antitumor, cytotoxic and antimicrobial activity: pharmacological evaluation of Knoevenagel condensate [beta]-diketone Schiff base thiosemicarbazone Cu(II) and Zn(II) complexes

Applied Organometallic Chemistry — Thu, 28 May 2009 04:00:00 +0100

Knoevenagel condensate Schiff base ligands [L = 3-cinnamalideneacetylacetone-thiosemicarbazone (CAT)/3-cinnama- lideneacetylacetoneethylthiosemicarbazone (CAET)/3-cinnamalideneacetylacetonephenylthiosemicarbazone (CAPT)] and their copper/zinc complexes were synthesized. They were characterized by analytical and spectral techniques. From these data it was found that the ligands adopt square-planar geometry on metalation with Cu2+ and Zn2+. To evaluate the antitumor and cytotoxic activity of the synthesized complexes in mice and human cancer cell lines, the antitumor activity of the complexes was evaluated against an Ehrlich ascites carcinoma (EAC) tumor model. The activity was assessed using survival time and short-term in vitro cytotoxic activity. Oral administration of complexes (100 mg/k...

Me3SiCl and Et3SiI-promoted one-pot synthesis of 1,4-dihydropyridine derivatives

Applied Organometallic Chemistry — Thu, 21 May 2009 04:00:00 +0100

An efficient synthesis of 1,4-dihydropyridine derivatives has been achieved by the one-pot cyclocondensation reaction of methyl 3-aminocrotonate and a range of aldehydes in the presence of chlorotrimethylsilane as a promoter under solvent-free conditions. The cyclocondenstion reaction requires a very short time and takes place in good to excellent yields. Furthermore iodotriethylsilane, generated in situ by the reaction of triethylsilane and methyl iodide in the presence of palladium chloride, has been investigated for the synthesis of 1,4-dihydropyridine derivatives. This facile and efficient method affords high yields for the preparation of 1,4-dihydropyridines at room temperature and short reaction times. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistr...

Hydrolysis of C,N-chelated diorganotin(IV) chlorides and catalysis of transesterification reactions

Applied Organometallic Chemistry — Tue, 19 May 2009 04:00:00 +0100

Diorganotin(IV) dichlorides of formula LCNRSnCl2 (where R is nBu or Ph) containing one LCN chelating ligand were hydrolyzed with aqueous sodium hydroxide in benzene. The composition of the products is strongly dependent on the amount of hydroxide. The partially hydrolyzed compounds of composition (LCNRSnCl)2(µ-O) were isolated as crystalline products. A hydrolysis where more than one molar equivalent of NaOH is employed gave only a mixture of unidentifiable products. The structure of (LCNPhSnCl)2(µ-O) was determined by X-ray diffraction techniques in the solid state. In solution there was a mixture of diastereoisomers found, where the tin atoms serve as a stereogenic centers. The catalytic activity of starting dichlorides as well as (LCNPhSnCl)2(µ-O) in various transesterification proce...

Regio- and stereospecific synthesis of polysubstituted alkenes by carbozincation of acetylenic sulfones

Applied Organometallic Chemistry — Tue, 19 May 2009 04:00:00 +0100

Tri- or tetrasubstituted alkenes with various substituents can be constructed regio- and stereospecifically by treatment of acetylenic sulfones with organozinc reagents in tetrahydrofuran followed by hydrolysis or coupling with halohydrocarbon. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Palladium-catalysed P[bond]C bond forming reactions between diphenylphosphine and ortho-substituted aryl bromides

Applied Organometallic Chemistry — Mon, 18 May 2009 04:00:00 +0100

The use of palladium catalysts derived from 1,1[prime]-bis-diisopropylphosphino-ferrocene and a microwave heating source allows the coupling of a range of ortho-substituted aryl bromides to diphenylphosphine derivatives to proceed in good yield in under 30 min. Optimization studies reveal that the combination of diphenylphosphine and DABCO is superior to more basic phosphide nucleophiles such as Ph2PK or Ph2PMgBr. High yields are only observed when moderately bulky electron rich diphosphines are used as ligands. The differences between P[bond]C coupling and other cross-coupling reactions are discussed in the light of the reactivity observed. Studies aimed at producing industrially important 1,2-bis-phosphino-benzene ligands are also described. Copyright © 2009 John Wiley & Sons, Ltd. (Sou...

UV-activated hydrosilylation: a facile approach for synthesis of hyperbranched polycarbosilanes

Applied Organometallic Chemistry — Mon, 18 May 2009 04:00:00 +0100

A facile approach for synthesis of hyperbranched polycarbosilane from AB2 monomer via UV-activated hydrosilylation is presented in this communication. The polymerization process was monitored using real-time FTIR spectroscopy and the resulting hyperbranched polycarbosilanes were characterized using 1H-NMR, 13C-NMR, 29Si-NMR and SEC/MALLS. It is found that hyperbranched polycarbosilane can be synthesized from methyldiallylsilane via UV-activated hydrosilylation with bis(acetylacetonato)platinum(II) as catalyst. The polymerization activated by UV irradiation was much faster than that under thermal conditions. The similar degree of branching, average number of branch units and the exponent of the Mark-Houwink equation demonstrate that the hyperbranched polycarbosilane synthesized via UV-activ...

Palladium bis(2,2,6,6-tetramethyl-3,5-heptanedionate) catalyzed alkoxycarbonylation and aminocarbonylation reactions

Applied Organometallic Chemistry — Fri, 15 May 2009 04:00:00 +0100

Palladium bis(2,2,6,6-tetramethyl-3,5-heptanedionate), a structurally well defined O-containing transition metal complex, is reported to be an efficient catalyst for alkoxycarbonylation and aminocarbonylation reactions under milder operating conditions. The system tolerated the carbonylative coupling of various aryl halides with phenol/alcohol and amines, providing good to excellent yields of desired products under optimized reaction conditions. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

A one-pot, stereoselective synthesis of 2-ethoxycarbonyl-substituted 1,3-dienes and 1,3-enynes by hydrostannylation-Stille tandem reaction of tributyltin hydride with alkynyl esters and alkenyl or alkynyl halides

Applied Organometallic Chemistry — Wed, 13 May 2009 04:00:00 +0100

2-Ethoxycarbonyl-substituted 1,3-dienes and 1,3-enynes can be stereoselectively synthesized in one pot under mild conditions, in good yields, by the palladium-catalyzed hydrostannylation of alkynyl esters, followed by Stille coupling with alkenyl or alkynyl halides, respectively. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

UV-visible spectroscopy for zirconocene activation by MAO in olefin polymerization: activity versus wavenumber

Applied Organometallic Chemistry — Wed, 13 May 2009 04:00:00 +0100

Activation of ansa-zirconocenes of the type Rac [Zr{1-Me2Si(3-R-([eta]5-C9H5))(3-R[prime]-([eta]5-C9H5))}Cl2] [R = Et, R[prime] = H (1); R = Pr, R[prime] = H (2); and R = Et, R[prime] = Pr (3), R, R[prime] = Me (4) and R, R[prime] = Bu (5)] by MAO has been studied by UV-visible spectroscopy. Compounds 1-3 have been tested in the polymerization of ethylene at different Al:Zr ratios. UV-vis spectroscopy was used to determine a correlation between the electronic structures of (1-5) and their polymerization activity. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Erick M. Carreira and Lisbet Kvaerno Classics in stereoselective synthesis Wiley-VCH, 2008, 651 pp. £ 60.00/£72.00 (paperback) 978-3-527-29966-9

Applied Organometallic Chemistry — Mon, 04 May 2009 04:00:00 +0100

No Abstract. (Source: Applied Organometallic Chemistry)

Palladium(II) and platinum(II) complexes of (1R,2R)-(-)-1,2-diaminocyclohexane (DACH) with various carboxylato ligands and their cytotoxicity evaluation

Applied Organometallic Chemistry — Sat, 11 Apr 2009 12:27:01 +0100

Several palladium(II) and platinum(II) complexes analogous to oxaliplatin, bearing the enantiomerically pure (1R,2R)-(-)-1,2-diaminocyclohexane (DACH) ligand, of the general formula {MX2[(1R,2R)-DACH]}, where M = Pd or Pt, X (COO)2, CH2(COO)2, , , {1,1[prime]-C5H8(CH2COO)2}, [1,1[prime]-C6H10(CH2COO)2], [1,1[prime]-(COO)2ferrocene], , , , MeCOO and Me3CCOO, were synthesized. All the complexes prepared were characterized physicochemically and spectroscopically. Some selected complexes were screened in vitro against several tumor cell lines and the results were compared with reference standard drug, oxaliplatin. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Hani Amouri and Michel Gruselle Chirality in transition metal chemistry: molecules, supramolecular assemblies and Materials Wiley, 2008, 260 pp. £37.50/[euro]46.90 0470060549 ISBN-13 9780470060544

Applied Organometallic Chemistry — Wed, 08 Apr 2009 04:00:00 +0100

No Abstract. (Source: Applied Organometallic Chemistry)

Synthesis and molecular structures of 1-boracyclopent-2-enes

Applied Organometallic Chemistry — Wed, 08 Apr 2009 04:00:00 +0100

The reaction of 1-silyl-1-borylalkenes with alkyn-1-yltin compounds affords borol-2-enes, organometallic-substituted allenes, mixtures thereof or even more complex mixtures with buta-1,3-dienes, depending on the third substituent at the C[double bond]C bond (Bu or Ph), on the number of Si[bond]Cl functions (two or three) and the nature of the alkyn-1-yltin compound. Six new borol-2-enes were isolated in pure state, and two of them were characterized by X-ray structural analysis. The solution-state structures of all major products were clearly established by multinuclear magnetic resonance methods (1H, 11B, 13C, 29Si, 119Sn NMR). Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Self-assembled three-dimensional flower-like [alpha]-Fe2O3 nanostructures and their application in catalysis

Applied Organometallic Chemistry — Wed, 08 Apr 2009 04:00:00 +0100

Three-dimensional flower-like [alpha]-Fe2O3 nanostructures have been successfully synthesized by a simple surfactant-free environmental friendly solvolthermal process. The as-prepared products were investigated by X-ray powder diffraction, transmission electron microscopy, and field emission scanning electron microscopy. By adjusting the synthetic parameters, the shape of the [alpha]-Fe2O3 nanostructures can be controlled. The three-dimensional flower-like [alpha]-Fe2O3 nanostructures were found to be highly active as catalysts for phenol alkylation. The effects of various parameters, such as reaction temperature, reaction time and the amount of catalyst, were studied. The catalyst was stable and could be reused three times in normal atmosphere without suffering appreciable loss in catalyt...

Deposition of osmium and ruthenium thin films from organometallic cluster precursors

Applied Organometallic Chemistry — Wed, 08 Apr 2009 04:00:00 +0100

Single-source organometallic precursors based on a number of homometallic clusters as well as heterometallic cluster RuOs3(CO)13(µ-H)2 have been used for the chemical vapor deposition of osmium films and osmium-ruthenium alloy films, respectively. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Preparation of N-alkylpyridinium aryl ketone derivatives via the surfactant promoted cross-coupling reaction of N-alkylpyridiniumboronic acids with carboxylic anhydride in water at room temperature

Applied Organometallic Chemistry — Wed, 08 Apr 2009 04:00:00 +0100

The palladium (II) chloride catalyzed coupling reaction of N-alkylpyridiniumboronic acids with benzoic anhydride was carried out smoothly in water to give high yields of ketones without the use of a phosphine ligand. The reaction was conducted under mild conditions at room temperature. In this article, by focusing on the Suzuki reaction, it is shown how this method can impact modern synthetic chemistry, making reactions faster, easier and cleaner. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Asymmetric transfer hydrogenation catalyzed by a novel planar chiral N-heterocyclic carbene-rhodium(I) complex

Applied Organometallic Chemistry — Wed, 08 Apr 2009 04:00:00 +0100

A novel chelated ferrocene-based planar chiral N-heterocyclic carbene-Rh(I) complex was synthesized by a simple method. It was applied to the asymmetric transfer hydrogenation of prochiral ketones. Enantioselectivities of up to 67% ee were observed. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Preparation and catalytic properties of bis(imino)pyridine palladium(II) complexes as efficient catalysts for Suzuki cross-coupling reaction in water

Applied Organometallic Chemistry — Wed, 18 Mar 2009 06:22:10 +0100

Air-stable bis(imino)pyridine palladium(II) complexes were synthesized and complex 12 proved to be a highly efficient catalyst for the Suzuki cross-coupling reaction between aryl bromides and arylboronic acids in air using water as solvent. The coupling reaction proceeded smoothly under mild conditions to provide biaryls in excellent yields and Pd black was not observed. The recycling of the catalysts was also investigated, for up to three cycles, and complex 12 still exhibited good activity. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Donald W. Braben Scientific Freedom: The Elixir of Civilization John Wiley & Sons; March 2008 184 pages; ISBN-10: 0-470-22654-4 ISBN-13: 978-0-470-22654-4

Applied Organometallic Chemistry — Mon, 16 Mar 2009 04:00:00 +0100

No Abstract. (Source: Applied Organometallic Chemistry)

ZrOCl2·8H2O: a highly efficient catalyst for the synthesis of 1,8-dioxo-octahydroxanthene derivatives under solvent-free conditions

Applied Organometallic Chemistry — Mon, 16 Mar 2009 04:00:00 +0100

ZrOCl2·8H2O has been found to be an efficient catalyst for the synthesis of 1,8-dioxo-octahydroxanthenes from aldehydes and 5,5-dimethylcyclohexane-1,3-dione under solvent-free conditions. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Hydrosilylation conditions applied on alkenyl benzylated xyloses: selective reduction and isomerization

Applied Organometallic Chemistry — Mon, 16 Mar 2009 04:00:00 +0100

In the presence of triethylsilane and different transition metal catalysts, the main reactive pathways observed from benzylated xyloses bearing an unsaturated tether were the reduction and the isomerization of the double bond without debenzylation of the sugar moiety. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

[Pt(topy)(Htopy)(ONO2)] complex (Htopy = 2-p-tolylpyridine) and its analogs: 195Pt NMR spectra and fabrication of light-emitting devices

Applied Organometallic Chemistry — Mon, 16 Mar 2009 04:00:00 +0100

We report fast, high-yield syntheses of a series of [Pt(C[and]N)(HC[and]N)X] complexes, where HC[and]N is 2-phenylpyridine (Hppy) or 2-p-tolylpyridine (Htopy) and X- is Cl-, Br-, I-, ONO2-, NO2- or SCN-. The structure of [Pt(topy)(Htopy)(ONO2)] was analyzed by single-crystal X-ray diffraction. Substitution of Cl- with Br- or I- in our complexes shifted the 195Pt NMR peaks upfield in the order Cl- < Br- < I-, but the magnitudes of their shifts were one-tenth those observed for non-cyclometalated platinum(II) complexes. As the two nitrato complexes showed strong emissions in acetonitrile solution - three to six times those of other complexes - they were used to fabricate OLEDs. Although their emissions were not particularly strong, devices fabricated with platinum(II) complexes containing bu...

Hemilabile-coordinated copper promoted amination of aryl halides with ammonia in aqueous ethylene glycol under atmosphere pressure

Applied Organometallic Chemistry — Mon, 16 Mar 2009 04:00:00 +0100

Direct amination of aryl iodides and bromides with ammonia under 1 atm pressure has been effected using in situ-generated hemilabile coordinated copper(I) species from copper(I) halides or copper metal in aqueous ethylene glycol, producing primary aromatic amines in good yields. Ammonia pressure and water were found to accelerate the copper-mediated reaction while strong chelating ligands showed a suppression effect. A rationale for the copper-mediated amination of aryl halides with ammonia is given based on a double-face role of chelating effect. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Ecofriendly synthesis, antimicrobial and antispermatogenic activity of triorganotin(IV) complexes with 4[prime]-nitrobenzanilide semicarbazone and 4[prime]-nitrobezanilide thiosemicarbazone

Applied Organometallic Chemistry — Mon, 16 Mar 2009 04:00:00 +0100

New series of triorganotin(IV) complexes with 4[prime]-nitrobenzanilide semicarbazone (L1H) and 4[prime]-nitrobenzanilide thiosemicarbazone (L2H) of the type [R3Sn(L)] (R = -CH3, -C6H5 and n-C4H9) were synthesized under microwave irradiation. All the complexes were characterized by elemental analysis, conductance measurements, molecular weight determinations and spectral data, viz., IR, UV-vis, 1H, 13C and 119Sn NMR. The central tin atoms of these complexes are all five-coordinated with trigonal bipyramidal geometry. In order to assess their growth inhibitory potency semicarbazone, thiosemicarbazone and their triorganotin(IV) complexes were tested in vitro against some pathogenic fungi and bacteria. Also the ligands and their organotin(IV) complexes were studied to assess the effects of lo...

Characteristic reactions of group 9 transition metal compounds in organic synthesis

Applied Organometallic Chemistry — Tue, 17 Feb 2009 22:22:37 +0100

Group 9 metal compounds in organic synthesis have two characteristic reactions. The first occurs because the group 9 metals have a high affinity to carbon-carbon or carbon-nitrogen [pi]-bonds. The first type of characteristic reactions in these group 9 metal compounds includes Pauson-Khand reactions, the Pauson-Khand-type reactions ([2 + 2 + 1] cyclization), the other cyclizations and coupling reactions. The second occurs because the group 9 metals have a high affinity to carbonyl groups. The second type of characteristic reactions includes carbonylations such as hydroformylations, the carbonylations of methanol, amidocarbonylations and other carbonylations. The first characteristic reactions are applied for the synthesis of fine chemicals such as pharmaceuticals and agrochemicals. However...

Ernesto Fattorusso and Orazio Tagialatela-Scafati (Eds). Modern alkaloids - structure, isolation, synthesis and biology Wiley-VCH; October 2007, 665 pp. ISBN 978-3-527-31521-5 (hardcover)

Applied Organometallic Chemistry — Mon, 16 Feb 2009 05:00:00 +0100

No Abstract. (Source: Applied Organometallic Chemistry)

John Emsley. Better looking, better living, better loving. How Chemistry can help you achieve life's goals Wiley-VCH, May 2007, 237 pp. (hardcover). ISBN-10 3-527-31863-1; ISBN-13 978-3-527-31863-6

Applied Organometallic Chemistry — Mon, 16 Feb 2009 05:00:00 +0100

No Abstract. (Source: Applied Organometallic Chemistry)

Synthesis and molecular structures of 1-chloro-1-silacyclopent-2-enes. Combination of 1,2-hydroboration, 1,1-organoboration and protodeborylation

Applied Organometallic Chemistry — Thu, 22 Jan 2009 05:00:00 +0100

The reaction of alkyn-1-yl(chloro)(methyl)vinyl- and alkyn-1-yl(chloro)(phenyl)-vinylsilane with 9-borabicyclo[3.3.1]nonane (9-BBN) afforded selectively 1-silacyclopent-2-ene derivatives containing a Si[bond]Cl function, as a result of consecutive 1,2-hydroboration and 1,1-organoboration. Protodeborylation with acetic acid left the Si[bond]Cl functions in various 1-silacyclopent-2-enes untouched, whereas acetic acid in the presence of dipropylamine led to conversion of the Si[bond]Cl into the Si[bond]OAc function. New starting materials and all products were characterized in solution by multinuclear NMR spectroscopy (1H, 11B, 13C and 29Si NMR), and the molecular structures of two 1-silacyclopent-2-ene derivatives were determined by X-ray analysis. The gas phase geometries of 1-silacyclopen...

Highly efficient bimetallic iron-palladium catalyzed Michael-type Friedel-Crafts reactions of indoles with chalcones

Applied Organometallic Chemistry — Sat, 03 Jan 2009 05:00:00 +0100

Iron-palladium is a superior bimetallic catalyst in the presence of acetylacetone (Acac) with remarkable synergistic effect for the Michael-type Friedel-Crafts reactions of indoles with chalcones. This catalytic system has the advantages of mild reaction conditions, smaller amount of metal salts, high yields of the desired products and operational simplicity, which make it a useful and promising process for the synthesis of indole derivatives. Copyright © 2009 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Synthesis and characterizations of N,N[prime]-bis(diphenylphosphino)-2-(aminomethyl)aniline derivatives: application of a palladium(II) complex as pre-catalyst in Heck and Suzuki cross-coupling reactions

Applied Organometallic Chemistry — Mon, 29 Dec 2008 05:00:00 +0100

The reaction of 2-(aminomethyl)aniline with 2 equivalents of PPh2Cl in the presence of Et3N, proceeds in CH2Cl2 to give N,N[prime]-bis(diphenylphosphino)-2-(aminomethyl)aniline 1 in good yield. Oxidation of 1 with aqueous H2O2, elemental sulfur or gray selenium gave the corresponding oxide, sulfide and selenide dichalcogenides [Ph2P(E)NHC6H4CH2NHP(E)Ph2] (E: O, 2a; S, 2b; Se, 2c), respectively. The reaction of [Ph2PNHC6H4CH2NHPPh2] with PdCl2(cod), PtCl2(cod) and [Cu(MeCN)4]PF6 gave the corresponding chelate complexes, PdCl21, PtCl21 and [Cu(1)2]PF6. The new compounds were fully characterized by NMR, IR spectroscopy and elemental analysis. The catalytic activity of the Pd(II) complex was tested in the Suzuki coupling and Heck reactions. The Pd(II) complex catalyzes the Suzuki coupling and ...

Metal and solvent-free cyanosilylation of carbonyl compounds with tris(pentafluorophenyl)borane

Applied Organometallic Chemistry — Sat, 20 Dec 2008 05:00:00 +0100

A highly effective method of the cynaosilylation of aldehydes and ketones with TMSCN in the presence of catalytic amount of B(C6F5)3 [tris(pentafluorophenyl)borane] has been developed. Cyano transfer from TMSCN to carbonyl group proceeds at room temperature under solvent-free conditions. Various alehydes and ketones have been converted into the corresponding trimethylsilylether within short reaction times with excellent yield under mild conditions. Copyright © 2008 John Wiley & Sons, Ltd. (Source: Applied Organometallic Chemistry)

Synthesis, characterization and catalytic studies of ruthenium(II) chalconate complexes

Applied Organometallic Chemistry — Thu, 18 Dec 2008 05:00:00 +0100

Stable ruthenium(II) carbonyl complexes of the type [RuCl(CO)(EPh3)(B)(L)] (E = P or As; B = PPh3, AsPh3 or Py; L = 2[prime]-hydroxychalcones) were synthesized from the reaction of [RuHCl(CO)(EPh3)2(B)] (E = P or As; B = PPh3, AsPh3 or Py) with 2[prime]-hydroxychalcones in benzene under reflux. The new complexes were characterized by analytical and spectroscopic (IR, electronic 1H, 31P and 13C NMR) data. They were assigned an octahedral structure. The complexes exhibited catalytic activity for the oxidation of primary and secondary alcohols into their corresponding aldehydes and ketones in the presence of N-methylmorpholine-N-oxide (NMO) as co-oxidant and were also found to be efficient transfer hydrogenation catalysts. Copyright © 2008 John Wiley & Sons, Ltd. (Source: Applied Organometal...