896 results match your criteria Organometallics [Journal]


Phosphino-Triazole Ligands for Palladium-Catalyzed Cross-Coupling.

Organometallics 2018 Nov 17;37(22):4224-4241. Epub 2018 Oct 17.

School of Chemistry and X-ray Crystallography Facility, School of Chemistry, University of Birmingham, Edgbaston, Birmingham, West Midlands B15 2TT, United Kingdom.

Twelve 1,5-disubtituted and fourteen 5-substituted 1,2,3-triazole derivatives bearing diaryl or dialkyl phosphines at the 5-position were synthesized and used as ligands for palladium-catalyzed Suzuki-Miyaura cross-coupling reactions. Bulky substrates were tested, and lead-like product formation was demonstrated. The online tool SambVca2. Read More

View Article
November 2018
1 Read

Vascular targeted nanotherapeutic approach for obesity treatment.

Int J Nanomedicine 2018 23;13:7915-7929. Epub 2018 Nov 23.

Department of Science and Technology/Mintek Nanotechnology Innovation Centre, Biolabels Unit, Department of Biotechnology, University of the Western Cape, Bellville, South Africa,

Obesity is a global epidemic that poses a serious health concern due to it being a risk factor for life-threatening chronic diseases, such as type 2 diabetes, cancer, and cardiovascular diseases. Pharmacotherapy remains the mainstay for the management of obesity; however, its usefulness is limited due to poor drug efficacy, non-specificity and toxic side effects. Therefore, novel approaches that could provide insights into obesity and obesity-associated diseases as well as development of novel anti-obesity treatment modalities or improvement on the existing drugs are necessary. Read More

View Article
November 2018

Water-soluble Ru(II)-anethole compounds with promising cytotoxicity toward the human gastric cancer cell line AGS.

Life Sci 2018 Dec 6. Epub 2018 Dec 6.

Laboratory of Organometallics, Department of Chemistry, Universidad Técnica Federico Santa María, Avenida España N° 1680, Valparaíso, Chile. Electronic address:

Aims: Ruthenium-based compounds exhibit critical biochemical properties making them suitable for diverse pharmacological applications. The aim of this work was to study the anticancer effects of three ruthenium complexes on a human gastric cancer cell line.

Main Methods: We synthetized three [Ru(η-anethole)(en)X]PF complexes, where (en) is ethylenediamine and X is Cl (1), Br (2) or I (3), which were then evaluated by MTT assay, RT-qPCR and flow cytometry on the human gastric cancer cell line AGS. Read More

View Article
December 2018

Structure-activity relationship of [1,5]azastibocines in cytotoxicity to vascular endothelial cells.

J Toxicol Sci 2018 ;43(12):735-740

Faculty of Pharmaceutical Sciences, Toho University.

It has been well established that organic-inorganic hybrid molecules can exhibit biological activities that are different from those of either their intramolecular metals in inorganic forms or their organic structures. We have previously reported that organoantimony compound Sb-phenyl-N-methyl-5,
6,7,12-tetrahydrodibenz[c,f][1,5]azastibocine (PMTAS) is nontoxic, but that the compound exhibits cytotoxicity in vascular endothelial cells when the antimony atom is replaced with a bismuth atom. In the present study, we investigated the cytotoxicity and intracellular accumulation of PMTAS and its analogs and found that the cytotoxicity of PMTAS analogs also decrease depending on the electron-withdrawing property of the substituent bound to the intramolecular antimony atom. Read More

View Article
January 2018
2 Reads

Nanostructure-induced performance degradation of WO·HO for energy conversion and storage devices.

Beilstein J Nanotechnol 2018 12;9:2845-2854. Epub 2018 Nov 12.

Center for Environmental and Energy Research, Ghent University Global Campus, Yeonsu-gu, Incheon 21985, South Korea.

Although 2D layered nanomaterials have been intensively investigated towards their application in energy conversion and storage devices, their disadvantages have rarely been explored so far especially compared to their 3D counterparts. Herein, WO·HO ( = 0, 1, 2), as the most common and important electrochemical and electrochromic active nanomaterial, is synthesized in 3D and 2D structures through a facile hydrothermal method, and the disadvantages of the corresponding 2D structures are examined. The weakness of 2D WO·HO originates from its layered structure. Read More

View Article
November 2018
3 Reads

Combined Effects of Backbone and N-Substituents on Structure, Bonding, and Reactivity of Alkylated Iron(II)-NHCs.

Organometallics 2018 Sep 6;37(18):3093-3101. Epub 2018 Sep 6.

Department of Chemistry, University of Rochester, Rochester, New York 14627, United States.

Iron and -heterocyclic carbenes (NHCs) have proven to be a successful pair in catalysis, with reactivity and selectivity being highly dependent on the nature of the NHC ligand backbone saturation and -substituents. Four (NHC)Fe(1,3-dioxan-2-ylethyl) complexes have been isolated and spectroscopically characterized to correlate their reactivity to steric effects of the NHC from the backbone saturation and -substituents. Only in the extreme case of SIPr where NHC backbone and -substituent steric effects are the largest is there a major structural perturbation observed crystallographically. Read More

View Article
September 2018

New Variations on the Theme of Gold(III) CNN Cyclometalated Complexes as Anticancer Agents: Synthesis and Biological Characterization.

Inorg Chem 2018 Nov 20. Epub 2018 Nov 20.

Dipartimento di Chimica e Farmacia , Università degli Studi di Sassari , via Vienna 2 , 07100 Sassari , Italy.

A series of novel (CNN) cyclometalated Au complexes of general formula [Au(bipy-H)X][PF] (bipy-H = CNN cyclometalated 6-(1,1-dimethylbenzyl)-2,2'-bipyridine) were prepared with a range of anionic ligands X in the fourth coordination position, featuring C (alkynyl)-, N-, O-, or S-donor atoms. The X ligands are varied in nature and include three coumarins, 4-ethynylaniline, saccharine, and thio-β-d-glucose tetraacetate, the tripeptide glutathione (GSH), and a coumarin-substituted amide derived from 4-ethynylaniline. The gold(I) complex [Au(CArNHCOQ)(PPh)] (HCArNHCOQ = N-(4-ethynylphenyl)-2-oxo-2 H-chromene-3-carboxamide) was also prepared for comparison. Read More

View Article
November 2018
4 Reads

Dataset on the development of palladium nanoparticle decorated colloidal porous organic polymer for photocatalytic Suzuki coupling.

Data Brief 2018 Dec 27;21:1157-1165. Epub 2018 Oct 27.

Laboratory of Organometallics, Catalysis and Ordered Materials, State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Center for Chemical and Material Engineering, Wuhan University of Technology, Wuhan 430070, China.

Herein, we report the synthesis and characterization data of visible-light-active colloidal azobenzene-based porous organic polymer (Azo-POP) and its Pd-nanoparticle loaded analog (Pd-Azo-POP). The setup for photocatalytic Suzuki reactions triggered by Pd-Azo-POP under conventional batch reaction mode as well as in a prototypal continuous flow system has also been provided in addition to the detailed catalytic data including H and C NMR spectra of the obtained products. For further discussions on the materials, their effect on overall catalysis and mechanistic insight, please refer to the associated article "Pd-nanoparticle decorated azobenzene-based colloidal porous organic polymer for visible and natural sunlight-induced Mott-Schottky junction mediated instantaneous Suzuki coupling" (Chakraborty et al. Read More

View Article
December 2018

Rhodium(III) and Iridium(III) Complexes of a NHC-Based Macrocycle: Persistent Weak Agostic Interactions and Reactions with Dihydrogen.

Organometallics 2018 Nov 9;37(21):3963-3971. Epub 2018 Oct 9.

Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, U.K.

The synthesis and characterization of five-coordinate rhodium(III) and iridium(III) 2,2'-biphenyl complexes [M(CNC-12)(biph)][BAr] (M = Rh (), Ir ()), featuring the macrocyclic lutidine- and NHC-based pincer ligand CNC-12 are reported. In the solid state these complexes are notable for the adoption of weak ε-agostic interactions that are characterized by ···H- contacts of ca. 3. Read More

View Article
November 2018
1 Read

Molecular Docking, Computational, and Antithrombotic Studies of Novel 1,3,4-Oxadiazole Derivatives.

Int J Mol Sci 2018 Nov 15;19(11). Epub 2018 Nov 15.

Institute of Chemistry, University of the Punjab, New Campus, Lahore 54590, Pakistan.

A new series of 1,3,4-oxadiazoles derivatives was synthesized, characterized, and evaluated for their in vitro and in vivo anti-thrombotic activity. Compounds (⁻) exhibited significant clot lysis with respect to reference drug streptokinase (30,000 IU), and enhanced clotting time (CT) values (130⁻342 s) than heparin (110 s). High affinity towards 1NFY with greater docking score was observed for the compounds (, , , , and ) than the control ligand RPR200095. Read More

View Article
November 2018

Metal Organic Frameworks Based Materials for Heterogeneous Photocatalysis.

Molecules 2018 Nov 12;23(11). Epub 2018 Nov 12.

Department of Chemistry, Center for Ordered Materials, Organometallics and Catalysis (COMOC), Ghent University, Krijgslaan 281 (S3), 9000 Gent, Belgium.

The increase in environmental pollution due to the excessive use of fossil fuels has prompted the development of alternative and sustainable energy sources. As an abundant and sustainable energy, solar energy represents the most attractive and promising clean energy source for replacing fossil fuels. Metal organic frameworks (MOFs) are easily constructed and can be tailored towards favorable photocatalytic properties in pollution degradation, organic transformations, CO₂ reduction and water splitting. Read More

View Article
November 2018
6 Reads

NH as traceless mediator for homo- and cross- aryl coupling.

Nat Commun 2018 11 9;9(1):4739. Epub 2018 Nov 9.

Department of Chemistry and FRQNT Center for Green Chemistry and Catalysis, McGill University, 801 Sherbrooke Street West, Montreal, QC, H3A 0B8, Canada.

Transition-metal catalyzed couplings of aryl halides or arenes with aryl organometallics, as well as direct reductive coupling of two aryl halides, are the predominant methods to synthesize biaryls. However, stoichiometric amounts of metals are inevitably utilized in these reactions, either in the pre-generation of organometallic reagents or acting as reductant in situ, thus producing quantitative metal waste. Herein, we demonstrate that this longstanding challenge can be overcome with NH as a metal surrogate. Read More

View Article
November 2018
2 Reads

Silver carbene complexes: An emerging class of anticancer agents.

Drug Dev Res 2018 Nov 1. Epub 2018 Nov 1.

University of Kansas Medical Center, Kansas City, Kansas.

Hit, Lead & Candidate Discovery Cancer is a major global health problem with large therapeutic challenges. Although substantial progress has been made in cancer therapy, there still remains a need to develop novel and effective treatment strategies to treat several relapsed and refractory cancers. Recently, there has been growing demand for considering organometallics as antineoplastic agents. Read More

View Article
November 2018
2 Reads

Mechanochemical routes for the synthesis of acetyl- and bis-(imino)pyridine ligands and organometallics.

Dalton Trans 2018 Dec 23;47(47):16876-16884. Epub 2018 Oct 23.

Department of Chemistry and the Energy Conversion and Propulsion Cluster, University of Central Florida, 4353 Scorpius Street, Orlando, FL 32816, USA.

Organometallic precatalysts play a pivotal role in organic synthesis. However, their preparation often relies on multiple time, energy, and solvent intensive steps, including the synthesis of supporting organic ligand structures, and finally installation on the desired metal centres. We report the sustainable mechanochemical synthesis of acetyl- and bis-(imino)pyridine pincer complexes, a ubiquitous ligand class for organometallic precatalysts. Read More

View Article
December 2018
4 Reads

Electrochemical transition-metal-catalyzed C-H bonds functionalization: electricity as clean surrogates of chemical oxidants.

ChemSusChem 2018 Oct 2. Epub 2018 Oct 2.

Qilu University of Technology (Shandong Academy of Science), School of Chemistry and Pharmaceutical Engineering, CHINA.

Transition-metal-catalyzed C-H activation attracts tremendous attentions in organic synthetic community because it obviates pre-functionalization of substrates.[1] Significant advances have been dedicated in the past several decades. However, it should be notated that super stoichiometric chemical oxidants, such as copper- or silver-based metal oxidants, benzoquinones (BQ), organic peroxides, potassium persulfate (K2S2O8), hypervalent iodine molecular oxygen (O2) and so on that are required for most of the reactions. Read More

View Article
October 2018
13 Reads

Single-Digit Nanometer Electron-Beam Lithography with an Aberration-Corrected Scanning Transmission Electron Microscope.

J Vis Exp 2018 Sep 14(139). Epub 2018 Sep 14.

Center for Functional Nanomaterials, Brookhaven National Laboratory;

We demonstrate extension of electron-beam lithography using conventional resists and pattern transfer processes to single-digit nanometer dimensions by employing an aberration-corrected scanning transmission electron microscope as the exposure tool. Here, we present results of single-digit nanometer patterning of two widely used electron-beam resists: poly (methyl methacrylate) and hydrogen silsesquioxane. The method achieves sub-5 nanometer features in poly (methyl methacrylate) and sub-10 nanometer resolution in hydrogen silsesquioxane. Read More

View Article
September 2018
1 Read

Synthesis of N-Heterocycle Substituted Silyl Ligands within the Coordination Sphere of Iron.

Organometallics 2018 Sep 10;37(18):3024-3034. Epub 2018 Sep 10.

Department of Chemistry, Debye Institute for Nanomaterials Science Utrecht University, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands.

N-Heterocycle-substituted silyl iron complexes have been synthesized by nucleophilic substitution at trichlorosilyl ligands bound to iron. The homoleptic (tripyrrolyl)- and tris(3-methylindolyl)silyl groups were accessed from (ClSi)CpFe(CO) (ClSiFp) by substitution of chloride with pyrrolide or 3-methylindolide, respectively. Analogously, nucleophilic substitution of Cl with pyrrolide on the anionic Fe(0) synthon ClSiFe(CO) generates the (tripyrrolyl)silyl ligand, bound to the iron tetracarbonyl fragment. Read More

View Article
September 2018

Organometallics and Catalysis.

Authors:
Clément Mazetto

Chimia (Aarau) 2018 Sep;72(9):577

University of Geneva Quai Ernest Ansermet 30 CH-1211 Geneva 4, Switzerland.

View Article
September 2018

Rare-Earth Cyclobutadienyl Sandwich Complexes: Synthesis, Structure and Dynamic Magnetic Properties.

Chemistry 2018 Nov 30;24(63):16779-16782. Epub 2018 Oct 30.

Department of Chemistry, School of Life Sciences, University of Sussex, Falmer, Brighton, BN1 9QJ, U.K.

The potassium cyclobutadienyl [K {η -C (SiMe ) }] (1) reacts with MCl (THF) (M=Y, Dy) to give the first rare-earth cyclobutadienyl complexes, that is, the complex anions [M{η -C (SiMe ) }{η -C (SiMe ) -κ-(CH SiMe }] , (2 ), as their dipotassium salts. The tuck-in alkyl ligand in 2 is thought to form through deprotonation of the "squarocene" complexes [M{η -C (SiMe ) } ] by 1. Complex 2 is a single-molecule magnet, but with prominent quantum tunneling. Read More

View Article
November 2018

Genetic diversity and biogeography of T. officinale inferred from multi locus sequence typing approach.

PLoS One 2018 18;13(9):e0203275. Epub 2018 Sep 18.

Laboratory of Drug Discovery and Molecular Engineering, Department of Medicinal Plants, College of Plant Science and Technology, Huazhong Agricultural University, Wuhan, China.

Taraxacum officinale (Asteraceae) is widely distributed weedy plant used as a traditional medicinal herb. The population genetics and historical biogeography of this plant have remained relatively unexplored. This study explores phylogeny, population genetics and ancestral reconstructions adopting multi locus sequence typing (MLST) approach. Read More

View Article
September 2018
1 Read
3.234 Impact Factor

TD DFT insights into unusual properties of excited sandwich complexes: structural transformations and vibronic interactions in Rydberg-state bis(η-benzene)chromium.

Phys Chem Chem Phys 2018 Oct 13;20(37):23988-23997. Epub 2018 Sep 13.

G.A. Razuvaev Institute of Organometallic Chemistry of the Russian Academy of Sciences, 49 Tropinin St., Nizhny Novgorod 603950, Russian Federation.

Sandwich compounds represent the only class of organometallics revealing vibronic structures of Rydberg transitions in their gas-phase absorption and ionization spectra. This provides rare possibilities of verifying computational results for Rydberg-state metal complexes by comparison with experimental spectroscopic data. In this work, the lowest Ryberg p state of bis(η-benzene)chromium (1) corresponding to the 3d→ R4p transition has been modeled for the first time by TD DFT. Read More

View Article
October 2018

Stoichiometry, polarity, and organometallics in solid-phase extracted dissolved organic matter of the Elbe-Weser estuary.

PLoS One 2018 5;13(9):e0203260. Epub 2018 Sep 5.

Alfred Wegener Institute Helmholtz Center for Polar and Marine Research, Bremerhaven, Germany.

Dissolved organic matter (DOM) is ubiquitous in natural waters and plays a central role in the biogeochemistry in riverine, estuarine and marine environments. This study quantifies and characterizes solid-phase extractable DOM and trace element complexation at different salinities in the Weser and Elbe River, northern Germany, and the North Sea. Dissolved organic carbon (DOC), total dissolved nitrogen (TDN), Co and Cu concentrations were analyzed in original water samples. Read More

View Article
September 2018
1 Read

Synthesis and characterization of chitosan-based waterborne polyurethane for textile finishes.

Carbohydr Polym 2018 Nov 25;200:54-62. Epub 2018 Jul 25.

Laboratory of Organometallics, Catalysis and Ordered Materials, State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China; National Research Tomsk Polytechnic University, Lenin Avenue 30, 634050 Tomsk, Russian Federation; Ghent University Global Campus Songdo, 119 Songdomunhwa-Ro, Yeonsu-Gu Incheon 406-840, South Korea. Electronic address:

Chitosan has gained an increased interest of researchers due to its nontoxic, biodegradable, biocompatible and renewable properties as well as its antimicrobial activity. In this work, a series of chitosan-based waterborne polyurethane (CS-WPU) emulsions were synthesized. The synthesis was accomplished by using a two-step emulsion polymerization process. Read More

View Article
November 2018

Bench-Stable Nickel Precatalysts with Heck-type Activation.

Organometallics 2018 Aug 9;37(16):2716-2722. Epub 2018 Aug 9.

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.

Herein, we report the synthesis and characterization of a new class of air- and moisture-stable phosphine-containing nickel(II) precatalysts, which activate through a Heck-type mechanism. The activities of the precatalysts are demonstrated with a carbonyl-ene coupling reaction. Read More

View Article

Tunable Metal⁻Organic Frameworks for Heat Transformation Applications.

Nanomaterials (Basel) 2018 Aug 26;8(9). Epub 2018 Aug 26.

National Research Tomsk Polytechnic University, Lenin Avenue 30, 634050 Tomsk, Russia.

Metal⁻Organic Frameworks (MOFs) are a subclass of porous materials that have unique properties, such as varieties of structures from different metals and organic linkers and tunable porosity from a structure or framework design. Moreover, modification/functionalization of the material structure could optimize the material properties and demonstrate high potential for a selected application. MOF materials exhibit exceptional properties that make these materials widely applicable in energy storage and heat transformation applications. Read More

View Article

Understanding the interactions of diruthenium anticancer agents with amino acids.

J Biol Inorg Chem 2018 Oct 25;23(7):1159-1164. Epub 2018 Jul 25.

School of Chemical Sciences, University of Auckland, Private Bag 92019, Auckland, 1142, New Zealand.

The dinuclear anticancer agents 1,n-bis{chlorido[3-(oxo-κO)-2-methyl-4-(1H)-pyridinonato-κO4](η-p-cymene)-ruthenium(II)}alkane (PyRu ) exhibit high antiproliferative activity in human cancer cell. Reactivity studies with DNA and protein revealed uncommon protein-DNA and DNA-DNA crosslinking ability. We report here studies on the reactions of the diruthenium organometallics PyRu and PyRu in comparison with a mononuclear analogue PyRu with amino acids using mass spectrometry and NMR spectroscopy. Read More

View Article
October 2018
22 Reads

Insights in Organometallic Synthesis of Various Adamantane Derivatives with Sigma Receptor-Binding Affinity and Antiproliferative/Anticancer Activity.

Methods Mol Biol 2018 ;1824:279-286

School of Health Sciences, Department of Pharmacy, Division of Pharmaceutical Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis-Zografou, Athens, 15784, Greece.

Organometallic reactions, such as those involving Grignard and organocadmium reagents, are very useful but require prudent laboratory skills. In many papers related to the medicinal chemistry of adamantane derivatives with sigma receptor (σR)-binding affinity and antiproliferative/anticancer activity, organometallics play a crucial role in the synthetic pathways. In this work, the experimental procedures utilizing Grignard and organocadmium reagents are presented in detail, because these techniques are not analyzed and are important in the rational drug design. Read More

View Article
January 2018

Fluorescent organometallic rhodium(I) and ruthenium(II) metallodrugs with 4-ethylthio-1,8-naphthalimide ligands: Antiproliferative effects, cellular uptake and DNA-interaction.

Eur J Med Chem 2018 Aug 25;156:148-161. Epub 2018 Jun 25.

Institute of Medicinal and Pharmaceutical Chemistry, Technische Universität Braunschweig, Beethoven Straße 55, 38106, Braunschweig, Germany. Electronic address:

Fluorescent 4-ethylthio-1,8-naphthalimides containing rhodium(I) N-heterocyclic carbene (NHC) and ruthenium (II) NHC fragments were synthesised and evaluated for their antiproliferative effects, cellular uptake and DNA-binding activity. Both types of organometallics triggered ligand dependent efficient cytotoxic effects against tumor cells with the rhodium(I) NHC derivatives causing stronger effects than the ruthenium (II) NHC analogues. Antiproliferative effects could also be observed against several pathogenic Gram-positive bacterial strains, whereas the growth of Gram-negative bacteria was not substantially affected. Read More

View Article
August 2018
4 Reads

Two tris-(3,5-disubstituted phen-yl)phosphines and their isostructural P oxides.

Acta Crystallogr E Crystallogr Commun 2018 Jul 5;74(Pt 7):889-894. Epub 2018 Jun 5.

Chemistry and Biochemistry, University of Lethbridge, 4401 University Drive West, Lethbridge, Alberta, T1K3M4, Canada.

The crystal structures of tris-(3,5-di-methyl-phen-yl)phosphine (CHP), (I), tris-(3,5-di-methyl-phen-yl)phosphine oxide (CHOP), (II), tris-(4-meth-oxy-3,5-di-methyl-phen-yl)phosphine (CHOP), (III), and tris-(4-meth-oxy-3,5-di-methyl-phen-yl)phosphine oxide (CHOP), (IV), are reported. The strucure of (III) has been described before [Romain (2000 ▸). , , 2047-2050], but it is rereported here on the basis of modern area-detector data and to facilitate comparison with the other structures reported here. Read More

View Article

A practical guide for using lithium halocarbenoids in homologation reactions.

Monatsh Chem 2018 11;149(7):1285-1291. Epub 2018 Jun 11.

Department of Pharmaceutical Chemistry, University of Vienna, Vienna, Austria.

Abstract: Lithium halocarbenoids are versatile reagents for accomplishing homologation processes. The fast α-elimination they suffer has been considered an important limitation for their extensive use. Herein, we present a series of practical considerations for an effective employment in the homologation of selected carbon electrophiles. Read More

View Article
June 2018
1 Read

Triorganoindium Reagents in Rh-Catalyzed C⁻H Activation/C⁻C Cross-Coupling Reactions of 2-Arylpyridines.

Molecules 2018 Jun 29;23(7). Epub 2018 Jun 29.

Centro de Investigaciones Científicas Avanzadas (CICA) and Departamento de Química, Universidade da Coruña, E-15071 A Coruña, Spain.

The activation of C⁻H bonds through catalytic reactions using transition metals is an important challenge in organic chemistry in which the intermediates are related to those produced in the classical cross-coupling reactions. As part of our research program devoted to the development of metal-catalyzed reactions using indium organometallics, a protocol for the C⁻H activation and C⁻C coupling of 2-arylpyridines with triorganoindium reagents under Rh(I) catalysis is reported. Under the optimized conditions, we found that Me₃In and Ar₃In reagents reacted with 2-arylpyridines and related compounds in the presence of Rh(PPh₃)₃Cl, in PhCl/THF (9:1), at 120 °C for 48 h, to afford the -coupling products in moderate to good yields. Read More

View Article
June 2018
1 Read

Tuning the Properties of Periodic Mesoporous Organosilica Films for Low-k Application by Gemini Surfactants.

Chemphyschem 2018 09 20;19(18):2295-2298. Epub 2018 Jun 20.

Kapeldreef 75, Leuven, 3001, Belgium.

Periodic mesoporous organosilica (PMO) thin films were synthesized by evaporation-induced self-assembly of 1,2-bis(triethoxysilyl)ethane and an ionic Gemini 16-12-16 surfactant under acidic conditions. The films were characterized by Fourier-transform infrared spectroscopy, grazing-incidence small-angle X-ray scattering, ellipsometric porosimetry, impedance measurements, and nanoindentation. The ease of control of the packing parameter in Gemini surfactants makes the PMO film templated by a Gemini an exciting first step towards small pore size PMO films with engineered mesostructures. Read More

View Article
September 2018
5 Reads

The Future of Polar Organometallic Chemistry Written in Bio-Based Solvents and Water.

Chemistry 2018 Oct 20;24(56):14854-14863. Epub 2018 Sep 20.

Dipartimento di Farmacia-Scienze del Farmaco, Università di Bari "Aldo Moro", Consorzio C.I.N.M.P.I.S., Via E. Orabona, 4, 70125, Bari, Italy.

There is a strong imperative to reduce the release of volatile organic compounds (VOCs) into the environment, and many efforts are currently being made to replace conventional hazardous VOCs in favour of safe, green and bio-renewable reaction media that are not based on crude petroleum. Recent ground-breaking studies from a few laboratories worldwide have shown that both Grignard and (functionalised) organolithium reagents, traditionally handled under strict exclusion of air and humidity and in anhydrous VOCs, can smoothly promote both nucleophilic additions to unsaturated substrates and nucleophilic substitutions in water and other bio-based solvents (glycerol, deep eutectic solvents), competitively with protonolysis, at room temperature and under air. The chemistry of polar organometallics in the above protic media is a complex phenomenon influenced by several factors, and understanding its foundational character is stimulating in the perspective of the development of a sustainable organometallic chemistry. Read More

View Article
October 2018
1 Read

Cationic nickel metal-organic frameworks for adsorption of negatively charged dye molecules.

Data Brief 2018 Jun 24;18:1952-1961. Epub 2018 Apr 24.

Laboratory of Organometallics, Catalysis and Ordered Materials, State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, PR China.

Industrial dye effluents with low biodegradability are highly toxic and carcinogenic on both human and aquatic lives, thus they are detrimental to the biodiversity of environment. Herein, this data set presents the potential of cationic Nickel based MOFs in the adsorption of charged and neutral dye molecules. Data set include a concise description of experimental conditions for the synthesis of imidazolium ligands, 1,3-bis(4-carboxyphenyl)imidazolium chloride (HLCl) and 1,3-bis(3,5-dicarboxyphenyl)imidazolium chloride (HLCl), and MOFs. Read More

View Article
June 2018
3 Reads

Transfer Hydrogenation and Antiproliferative Activity of Tethered Half-Sandwich Organoruthenium Catalysts.

Organometallics 2018 May 23;37(10):1555-1566. Epub 2018 Apr 23.

Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, U.K.

We report the synthesis and characterization of four neutral organometallic tethered complexes, [Ru(η-Ph(CH)-ethylenediamine--R)Cl], where R = methanesulfonyl (Ms, ), toluenesulfonyl (Ts, ), 4-trifluoromethylbenzenesulfonyl (Tf, ), and 4-nitrobenzenesulfonyl (Nb, ), including their X-ray crystal structures. These complexes exhibit moderate antiproliferative activity toward human ovarian, lung, hepatocellular, and breast cancer cell lines. Complex in particular exhibits a low cross-resistance with cisplatin. Read More

View Article
May 2018
9 Reads

DFT Investigation of Suzuki-Miyaura Reactions with Aryl Sulfamates Using a Dialkylbiarylphosphine-Ligated Palladium Catalyst.

Organometallics 2017 Sep 13;36(18):3664-3675. Epub 2017 Sep 13.

Hylleraas Centre for Quantum Molecular Sciences, Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, Oslo 0315, Norway.

Aryl sulfamates are valuable electrophiles for cross-coupling reactions because they can easily be synthesized from phenols and can act as directing groups for C-H bond functionalization prior to cross-coupling. Recently, it was demonstrated that (1-Bu-Indenyl)Pd(XPhos)Cl (XPhos = 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl) is a highly active precatalyst for room-temperature Suzuki-Miyaura couplings of a variety of aryl sulfamates. Herein, we report an in-depth computational investigation into the mechanism of Suzuki-Miyaura reactions with aryl sulfamates using an XPhos-ligated palladium catalyst. Read More

View Article
September 2017
1 Read

Stereoselectivity Switch in the Trapping of Polar Organometallics with Andersen's Reagent-Access to Highly Stereoenriched Transformable Biphenyls.

J Org Chem 2018 Aug 13;83(15):7751-7761. Epub 2018 Jun 13.

Université de Strasbourg , Université de Haute-Alsace, CNRS, LIMA UMR 7042, ECPM , 25 rue Becquerel , F-67000 Strasbourg , France.

The trapping of racemic polar carbometallic species with (-)-menthyl ( S)- p-toluenesulfinate (Andersen's reagent) typically proceeds with a very low level of resolution. In this paper, we describe a strategy that allows access to highly atropo-enriched and functionalizable biphenyls by means of Andersen's reagent under kinetic resolution conditions. In particular, useful enantiopure 2-iodobiphenyls could be obtained and were employed in a challenging hypervalent iodine-catalyzed oxidation reaction. Read More

View Article
August 2018
9 Reads

High-Z Sensitized Plastic Scintillators: A Review.

Adv Mater 2018 Jul 7;30(27):e1706956. Epub 2018 May 7.

UCLA Department of Materials Science and Engineering, 420 Westwood PlazaEngineering V Room 3111, Los Angeles, CA, 90095, USA.

The need for affordable and reliable radiation detectors has prompted significant investment in new radiation detector materials, due to concerns about national security and nuclear nonproliferation. Plastic scintillators provide an affordable approach to large volume detectors, yet their performance for high-energy gamma radiation is severely limited by the small radiation stopping power inherent to their low atomic number. Although some sensitization attempts with organometallics were made in the 1950s to 1960s, the concomitant decrease in light yield has limited the usefulness of these sensitized detectors. Read More

View Article
July 2018
2 Reads

Peptide-functionalized quantum dots for potential applications in the imaging and treatment of obesity.

Int J Nanomedicine 2018 27;13:2551-2559. Epub 2018 Apr 27.

Department of Science and Technology (DST)/Mintek Nanotechnology Innovation Centre, Biolabels Unit, Department of Biotechnology.

Background: Obesity is a worldwide epidemic affecting millions of people. The current pharmacological treatment of obesity remains limited and ineffective due to drugs' undesirable side effects. Hence, there is a need for novel or improved strategies for long-term therapies that will help prevent the disease progression into other chronic diseases. Read More

View Article

Stabilized Vanadium Catalyst for Olefin Polymerization by Site Isolation in a Metal-Organic Framework.

Angew Chem Int Ed Engl 2018 Jul 30;57(27):8135-8139. Epub 2018 May 30.

Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA, 02139, USA.

Vanadium catalysts offer unique selectivity in olefin polymerization, yet are underutilized industrially owing to their poor stability and productivity. Reported here is the immobilization of vanadium by cation exchange in MFU-4l, thus providing a metal-organic framework (MOF) with vanadium in a molecule-like coordination environment. This material forms a single-site heterogeneous catalyst with methylaluminoxane and provides polyethylene with low polydispersity (PDI≈3) and the highest activity (up to 148 000 h ) reported for a MOF-based polymerization catalyst. Read More

View Article
July 2018
4 Reads

Half-Sandwich Arene Ruthenium(II) and Osmium(II) Thiosemicarbazone Complexes: Solution Behavior and Antiproliferative Activity.

Organometallics 2018 Mar 20;37(6):891-899. Epub 2018 Feb 20.

Dipartimento di Scienze Chimiche, della Vita e della Sostenibilità Ambientale and CIRCMSB (Consorzio Interuniversitario di Ricerca in Chimica dei Metalli nei Sistemi Biologici), University of Parma, Parco Area delle Scienze 11/A, 43124 Parma, Italy.

We report the synthesis, characterization, and antiproliferative activity of organo-osmium(II) and organo-ruthenium(II) half-sandwich complexes [(η--cym)Os(L)Cl]Cl ( and ) and [(η--cym)Ru(L)Cl]Cl ( and ), where L = -(2-hydroxy)-3-methoxybenzylidenethiosemicarbazide () or -(2,3-dihydroxybenzylidene)-3-phenylthiosemicarbazide (), respectively. X-ray crystallography showed that all four complexes possess half-sandwich pseudo-octahedral "three-legged piano-stool" structures, with a neutral N,S-chelating thiosemicarbazone ligand and a terminal chloride occupying three coordination positions. In methanol, / isomerization of the coordinated thiosemicarbazone ligand was observed, while in an aprotic solvent like acetone, partial dissociation of the ligand occurs, reaching complete displacement in a more coordinating solvent like DMSO. Read More

View Article
March 2018
2 Reads

Removal of arsenic and mercury species from water by covalent triazine framework encapsulated γ-FeO nanoparticles.

J Hazard Mater 2018 Jul 16;353:312-319. Epub 2018 Apr 16.

Department of Chemistry, Center for Ordered Materials, Organometallics and Catalysis (COMOC), Faculty of Sciences, Ghent University, Krijgslaan 281 (S3), 900 Ghent, Belgium. Electronic address:

The covalent triazine framework, CTF-1, served as host material for the in situ synthesis of FeO nanoparticles. The composite material consisted of 20 ± 2 m% iron, mainly in γ-FeO phase. The resulting γ-FeO@CTF-1 was examined for the adsorption of As, As and Hg from synthetic solutions and real surface-, ground- and wastewater. Read More

View Article
July 2018
12 Reads

Concurrent reduction-adsorption of chromium using m-phenylenediamine-modified magnetic chitosan: kinetics, isotherm, and mechanism.

Environ Sci Pollut Res Int 2018 Jun 20;25(18):17830-17841. Epub 2018 Apr 20.

Laboratory of Organometallics, Catalysis and Ordered Materials, State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, 430070, People's Republic of China.

Magnetic chitosan particles (MCS) were chemically grafted by m-phenylenediamine (mPD) forming a distinctive shell layer with abundant nitrogenous functional groups and used as an adsorbent for the effective removal of Cr(VI) from aqueous solution. By interaction among functional groups in the facile oxidative polymerization process, the grafting of mPD and its polymers on MCS surface was innovatively realized. Through Fourier-transformed infrared spectroscopy, energy dispersive spectrometer, X-ray photoelectron spectroscopy, etc. Read More

View Article
June 2018
5 Reads

Exploring Lanthanide Doping in UiO-66: A Combined Experimental and Computational Study of the Electronic Structure.

Inorg Chem 2018 May 16;57(9):5463-5474. Epub 2018 Apr 16.

Center for Molecular Modeling (CMM) , Ghent University , Technologiepark 903 , 9052 Zwijnaarde , Belgium.

Lanthanide-based metal-organic frameworks show very limited stabilities, which impedes their use in applications exploiting their extraordinary electronic properties, such as luminescence and photocatalysis. This study demonstrates a fast and easy microwave procedure to dope UiO-66, an exceptionally stable and tunable Zr-based metal-organic framework. The generally applicable synthesis methodology is used to incorporate different transition metal and lanthanide ions. Read More

View Article
May 2018
2 Reads

Luminescent Lanthanide MOFs: A Unique Platform for Chemical Sensing.

Materials (Basel) 2018 Apr 7;11(4). Epub 2018 Apr 7.

Department of Chemistry, Center for Ordered Materials, Organometallics and Catalysis (COMOC), Ghent University, Krijgslaan 281 (S3), 9000 Gent, Belgium.

In recent years, lanthanide metal-organic frameworks (LnMOFs) have developed to be an interesting subclass of MOFs. The combination of the characteristic luminescent properties of Ln ions with the intriguing topological structures of MOFs opens up promising possibilities for the design of LnMOF-based chemical sensors. In this review, we present the most recent developments of LnMOFs as chemical sensors by briefly introducing the general luminescence features of LnMOFs, followed by a comprehensive investigation of the applications of LnMOF sensors for cations, anions, small molecules, nitroaromatic explosives, gases, vapors, pH, and temperature, as well as biomolecules. Read More

View Article
April 2018
2 Reads

Do dihydroxymagnesium carboxylates form Grignard-type reagents? A theoretical investigation on decarboxylative fragmentation.

J Mol Model 2018 Mar 27;24(4):106. Epub 2018 Mar 27.

Analytical BioGeoChemistry, Helmholtz Zentrum München, Munich, Germany.

Dihydroxymagnesium carboxylates [(OH)MgOCR] were probed for decarboxylation on a theoretical level, by utilizing both Møller-Plesset perturbation theory (MP2) and density functional theory (B3LYP-DFT) computations. This study is connected to the question of whether this recently introduced, astrobiologically relevant chemical class may form Grignard-type reagent molecules. To extract trends for a broad molecular mass range, different linear alkyl chain lengths between C and C were computed. Read More

View Article
March 2018
10 Reads

Long-Range Corrected DFT Calculations of First Hyperpolarizabilities and Excitation Energies of Metal Alkynyl Complexes.

Chemphyschem 2018 06 2;19(12):1537-1546. Epub 2018 May 2.

Research School of Chemistry, Australian National University, Canberra, ACT 2601, Australia.

The performance of the CAM-B3LYP, ωB97X and LC-BLYP long-range corrected density functional theory methods in the calculation of molecular first hyperpolarizabilities (β) and low-lying charge transfer (CT) excitation energies of the metal alkynyl complexes M(C≡C-4-C H -1-NO )(κ -dppe)(η -C H ) [M=Fe (1), Ru (2), Os (3)] and trans-[Ru{C≡C-(1,4-C H C≡C) -4-C H -1-NO }Cl(κ -dppm) ] [n=0 (4), 1 (5), 2 (6)] was assessed. The BLYP, B3LYP and PBE0 standard exchange-correlation functionals and the Hartree-Fock method were also examined. The BLYP functional was shown to perform poorly in the calculation of β and low-energy CT transitions. Read More

View Article
June 2018
25 Reads

Role of σ,π-Digold(I) Alkyne Complexes in Reactions of Enynes.

Organometallics 2018 Mar 19;37(5):781-786. Epub 2017 Dec 19.

Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain.

Gold(I) acetylide and σ,π-digold(I) alkyne complexes derived from one prototypical 1,6-enyne and from 7-ethynyl-1,3,5-cycloheptatriene have been prepared and structurally characterized. Their possible role in gold(I)-catalyzed cycloisomerizations has been studied by experiment and by DFT calculations. Gold(I) acetylides are totally unproductive complexes in the absence of Brønsted acids. Read More

View Article
March 2018
2 Reads

Dinuclear Nickel Complexes of Thiolate-Functionalized Carbene Ligands and Their Electrochemical Properties.

Organometallics 2018 Mar 4;37(5):740-747. Epub 2017 Oct 4.

Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.

Four dimeric nickel(II) complexes [NiCl(BnCS)] [], [NiCl(BnCS)] [], [Ni(PyCS)]Br []Br, and [Ni(PyCS)]Br []Br of four different thiolate-functionalized N-heterocyclic carbene (NHC) ligands were synthesized, and their structures have been determined by single-crystal X-ray crystallography. The four ligands differ by the alkyl chain length between the thiolate group and the benzimidazole nitrogen (two -C- or three -C- carbon atoms) and the second functionality at the NHC being a benzyl (Bn) or a pyridylmethyl (Py) group. The nickel(II) ions are coordinated to the NHC carbon atom and the pendent thiolate group, which bridges to the second nickel(II) ion creating the dinuclear structure. Read More

View Article
March 2018
2 Reads

Iridium and Ruthenium Complexes of -Heterocyclic Carbene- and Pyridinol-Derived Chelates as Catalysts for Aqueous Carbon Dioxide Hydrogenation and Formic Acid Dehydrogenation: The Role of the Alkali Metal.

Organometallics 2017 Mar 3;36(6):1091-1106. Epub 2017 Mar 3.

Department of Chemistry, The University of Alabama, Box 870336, Tuscaloosa, Alabama 35487-0336, United States.

Hydrogenation reactions can be used to store energy in chemical bonds, and if these reactions are reversible, that energy can be released on demand. Some of the most effective transition metal catalysts for CO hydrogenation have featured pyridin-2-ol-based ligands (e.g. Read More

View Article
March 2017
25 Reads