Search results for "Hydride"
showing 10 items of 322 documents
Protonation and oxidation chemistry of a pentaethylcyclopentadienyl-containing molybdenum(IV) trihydride complex
2000
International audience; Compound CpEtMoCl4 (CpEt=η5-C5Et5) (1) can be transformed into CpEtMoH3(dppe) (2) and CpEtMoD3(dppe) (2-d3) [dppe=1,2-(diphenylphosphino)ethane] by reaction with LiAlX4 (X=H and D, respectively). The protonation and oxidation studies of these two compounds, in comparison with previously reported studies on (C5Me5) analogs, show important differences that may be attributed to a kinetic stabilization of the products, which is steric in nature. Protonation of 2 with HBF4 in acetonitrile affords [CpEtMoH4(dppe)]+ (3), which only slowly decomposes to [CpEtMoH2(MeCN)(dppe)]+ (4). Further protonation of the latter affords the monohydride species [Cp*MoH(dppe)(MeCN)2]2+ in t…
A Computational Study of Ethylene C−H Bond Activation by [Cp*Ir(PR3)]
2001
It has previously been demonstrated that both [(C5Me5)Ir(PMe3)(CH=CH2)H] and [(C5Me5)Ir(PMe3)(H2C=CH2)] are formed when [(C5Me5)Ir(PMe3)] is thermolytically generated in the presence of ethylene. At higher temperatures, the vinyl hydride is converted to the eta2-ethylene adduct. Density functional theory has now been used to investigate this reaction, using the B3LYP functional, two types of basis sets (LanL2DZ and TZV*), and two models of the [(C5R5)Ir(PR3)] species (R=H and CH3). The study consists of full optimizations of local minima, first-order saddle points, and minimum energy crossing points (MECP). The experimental results are best accounted for by considering both singlet and trip…
Hydrogels for potential colon drug release by thiol-ene conjugate addition of a new inulin derivative.
2008
Inulin was chosen as a starting polymer for biocompatible, pH-sensitive and biodegradable hydrogels. Three INUDVSA-TT hydrogels were obtained by crosslinking inulin derivatives with trimethylolpropane tris(3-mercaptopropionate) under varying conditions. The resulting hydrogels were cell compatible, as demonstrated by MTS and trypan blue exclusion assays acting on Caco-2 cells, and were biodegraded by inulinase and esterase, thus suggesting their use as colonic drug delivery systems. 2-Methoxyestradiol, an anti-cancer drug, was soaked in INUDVSA-TT hydrogels and its in vitro release and apoptotic effect on Caco-2 cells were evaluated.
Studium zum Vorgang der Wasserstoffübertragung, 50. Elektroreduktion und phasentransferkatalysierte Borhydrid-reduktion prochiraler Ketone
1978
Prochirale Carbonylverbindungen wurden in die entsprechenden sekundaren Alkohole ubergefuhrt a) durch Elektroreduktion und b) mit NaBH4, in beiden Fallen mit den gleichen Ephedriniumsalzen, und zwar fur a) als optisch aktive Leitsalze und fur b) als optisch aktive Phasentransfer-Katalysatoren. Es wurden bei der Elektroreduktion und bei der Phasentransfer-Katalyse die Ausbeuten an Carbinol (und Pinakol)3), die optische Ausbeute und die absolute Konfiguration des bevorzugt gebildeten Enantiomeren bestimmt. In der uberwiegenden Mehrzahl der untersuchten Beispiele besitzen die unter Mitwirkung optisch aktiver Ephedriniumsalze nach beiden Methoden erhaltenen Uberschusenantiomeren die entgegenges…
Thermochromic Fluorescence from B18H20(NC5H5)2: An Inorganic–Organic Composite Luminescent Compound with an Unusual Molecular Geometry
2017
BH(NCH) is a rare example of two conjoined boron hydride subclusters of nido and arachno geometrical character. At room temperature, solutions of BH(NCH) emit a 690 nm fluorescence. In the solid state, this emission is shifted to 620 nm and intensifies due to restriction of the rotation of the pyridine ligands. In addition, there is a thermochromicity to the fluorescence of BH(NCH). Cooling to 8 K engenders a further shift in the emission wavelength to 585 nm and a twofold increase in intensity. Immobilization in a polystyrene thin-film matrix results in an efficient absorption of pumping excitation energy at 414 nm and a 609 nm photostable fluorescence. Such fluorescence from polystyrene t…
An efficient acetylation of dextran using in situ activated acetic anhydride with iodine
2010
A facile, efficient, cost-effective and solvent-free acetylation method has been developed for the acetylation of dextran. Dextran acetates were successfully synthesized using different molar ratios of acetic anhydride in the presence of iodine as a catalyst without the use of any solvent. The reactions were realized at 50?C for 3 h under stirring and nitrogen. This efficient method yielded highly pure and organosoluble dextran esters. The reaction appears highly effective for obtaining higher degrees of substitution (DS) with great efficiency. Under solvent-free conditions, dextran triacetates were efficiently synthesized. It was also observed that the molar ratio can easily control the DS…
Fullerene-ionic-liquid conjugates: a new class of hybrid materials with unprecedented properties.
2015
A modular approach has been followed for the synthesis of a series of fullerene-ionic-liquid (IL) hybrids in which the number of IL moieties (two or twelve), anion, and cation have been varied. The combination of C60 and IL give rise to new unique properties in the conjugates such as solubility in water, which was higher than 800 mg mL(-1) in several cases. In addition, one of the C60 -IL hybrids has been employed for the immobilization of palladium nanoparticles through ion exchange followed by reduction with sodium borohydride. Surprisingly, during the reduction several carbon nanostructures were formed that comprised nano-onions and nanocages with few-layer graphene sidewalls, which have…
Estimation of hydrogen transfer mechanisms in composite materials
2008
Abstract Spill-over effect as a hydrogen transfer mechanism is proposed to explain an increased capacity of hydrogen absorption and improvement of hydrogen activation kinetics in composite material based on the AB5 type metal hydride and powdered glass. A raw lanthanum nickel alloy AB5 with small amount of additives was used as catalyst and bulk material for hydrogen storage, and a borosilicate glass powder with developed surface was applied as a support material. Thermogravimetric technique to determine an absorbed amount of the hydrogen in materials and X-ray powder diffraction analysis for structural investigations was used.
Straightforward preparation of highly loaded MWCNT-polyamine hybrids and their application in catalysis
2020
Multiwalled carbon nanotubes (MWCNTs) were easily and efficiently functionalised with highly cross-linked polyamines. The radical polymerisation of two bis-vinylimidazolium salts in the presence of pristine MWCNTs and azobisisobutyronitrile (AIBN) as a radical initiator led to the formation of materials with a high functionalisation degree. The subsequent treatment with sodium borohydride gave rise to the reduction of imidazolium moieties with the concomitant formation of secondary and tertiary amino groups. The obtained materials were characterised by thermogravimetric analysis (TGA), elemental analysis, solid state 13C-NMR, Fourier-transform infrared spectroscopy (FT-IR), transmission ele…
Configurational landscape of chiral iron(II) bis(phosphane) complexes
2020
[EN] The reaction of a chiral [FeH(¿2-H2){(R,R)-Me-DuPhos}2]+ ((R,R)-Me-DuPhos = (¿)-1,2-bis[(2R,5R)-2,5-dimethylphospholano]benzene) complex with ethers and halides is investigated by NMR techniques. From this study, it is apparent that dihydrogen ligand exchange by poorly-coordinating donor molecules, such as THF or Et2O, is feasible under mild conditions. The cis-[FeH(THF-d8){(R,R)-Me-DuPhos}2]+ complex is identified as the product in THF-d8 solution. A mixture of cis- and trans-[FeH(ether){(R,R)-Me-DuPhos}2]+ isomers is obtained after the addition of small quantities of THF or Et2O to a CD2Cl2 solution of [FeH(¿2-H2){(R,R)-Me-DuPhos}2]+. The reaction of [FeH(¿2-H2){(R,R)-Me-DuPhos}2]+ w…