Search results for "Lithium"
showing 10 items of 680 documents
Synthesis of borylindenides; structure of [Li(N,N′,N″-Me3-1,3,5-C3H6N3)][1-C9H6{B(NMe2)2}]
1998
Abstract Borylation of lithium indenide (LiInd) affords indenylboranes. With BCl(NMe2)2 the primary allylic 1-indenyl derivative IndB(NMe2)2 (1) readily rearranges to the more stable vinylic bis(dimethylamino)(3-indenyl)borane 1′. With BCl(OCMe2)2 the (1-indenyl)-1,3,2-dioxaborolane IndB(OCMe2)2 (2) is obtained. Both indenylboranes 1′ and 2 readily undergo metalation when treated with lithium amides such as LiTMP or LDA to give 1-borylindenides Li[C9H6B(NMe2)2] [Li(3)] and Li[C9H6B(OCMe2)2] [Li(5)] in high yields. In the systems 1′/LiInd and 2/LiInd metalation equilibria are established with equlibrium constants K≈1 (1'/LiInd) and K≈1.4 (2/LiInd). The structure of the solvate [Li(TMHT)][1-C…
P-Chirogenic Phosphines Supported by Calix[4]arene: New Insight into Palladium-Catalyzed Asymmetric Allylic Substitution
2013
The first P-chirogenic mono- and diphosphine ligands supported on the upper rim of a calix[4]arene moiety were synthesized using the ephedrine methodology. The lithiated calix[4]arene mono- and dianions both react with the oxazaphospholidine–borane, prepared from ephedrine, to afford regio- and stereoselectively the corresponding calix[4]arenyl aminophosphine–boranes, by cleavage of the heterocyclic ring at the P–O bond position. Subsequent reactions with HCl and then organolithium reagent and finally decomplexation with DABCO lead to the corresponding calix[4]arenyl mono- or diphosphines. Both enantiomers of the calix[4]arenyl phosphines were obtained either by using (+)- or (−)-ephedrine …
ChemInform Abstract: Enediolates and Dienediolates of Carboxylic Acids in Synthesis. Synthesis of β,γ-Epoxyacids from α-Chloroketones.
2010
Abstract Lithium dienolates of saturated or α,β-unsaturated acids react with α-chloroketones provide a convenient method for preparation of highly sustituted β,γ-epoxyacids. These highly reactive compounds lead in most cases to variable ammounts of the corresponding β-lactones and allylic alcohols.
Cyclopentadienylmolybdenum(II) and -(III) complexes containing diene and allyl ligands. Part 4. Reactivity studies of the bisallyl complex CpMo(supin…
1998
Abstract Compound CpMo( η 3 -C 3 H 5 ) 2 , 3, has been synthesized from CpMoCl 4 and four equivalents of allylmagnesium bromide. While the compound is stable in donor solvents at room temperature, warming in refluxing MeCN induces the formation of 1,5-hexadiene by a metal-mediated allyl-allyl coupling process. Treatment of 3 with Bu t NC at room temperature affords CpMo( η 3 -C 3 H 5 )(Bu t NC) 2 , 4. A similar reduction with presumed allyl radical loss occurs for [CpMo( η 3 -C 3 H 5 )( η 4 -C 4 H 6 )] + , [1c] + , to afford [CpMo( η 4 -C 4 H 6 )(Bu t NC) 2 ] + , 5. Treatment of [1c] + with methyllithium affords two products, the major one (1c) corresponding to the one-electron reduction pa…
Efficient Addition of Acid Enediolates to Epoxides
2004
We report new conditions to facilitate the addition of dianions of carboxylic acids to epoxides as an alternative method to the use of aluminum enolates. These conditions require the use of a sub-stoichiometric (10%) amount of amine for dianion generation and the previous activation of the epoxide with LiCl. Other Lewis acids have been shown to be less effective. Yields are good but only low diastereoselectivity is attained, which has not been controlled despite attempts at optimization. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
On the nature of phase separation in a commercial aluminium-lithium alloy
1996
Abstract The formation of lithium-rich precipitate particles, known as δ′ phase, is responsible for the particularly desirable mechanical properties which make aluminium-lithium alloys interesting for different industrial applications. The structure and the kinetics of the phase separation process are conveniently studied by small-angle X-ray scattering, though uncertainties remain on the actual shape of the phase diagram of the system, particularly in the region of interest. In this paper are reported small-angle X-ray scattering measurements on a commercial AlLi (8.49% Li atoms) both in the region of formation of the precipitate and during its successive growth. Modelling of the experime…
Amorphous Silicon Nanotubes via Galvanic Displacement Deposition
2013
Amorphous silicon nanotubes were grown in a single step into a polycarbonate membrane by a galvanic displacement reaction conducted in aqueous solution. In order to optimize the process, a specifically designed galvanic cell was used. SEM images, after polycarbonate dissolution, showed interconnected nanotube bundles with an average length of 18 μm and wall thickness of 38 nm.The deposited silicon was revealed by EDS analysis, whilst X-ray diffraction and Raman spectroscopy showed that nanotubes have an amorphous structure. Silicon nanotubes were also characterized by photo-electrochemical measurements that showed n-type conductivity and optical gap of ~1.6 eV. Keywords: Silicon nanotubes, …
Control of signal coherence in parametric frequency mixing with incoherent pumps: Narrowband mid-infrared light generation by downconversion of broad…
2012
International audience; We study, with numerical simulations using the generalized nonlinear envelope equation, the processes of optical parametric and difference- and sum-frequency generation (SFG) with incoherent pumps in optical media with both quadratic and third-order nonlinearity, such as periodically poled lithium niobate. With ultrabroadband amplified spontaneous emission pumps or continua (spectral widths > 10 THz), group-velocity matching of a near-IR pump and a short-wavelength mid-IR (MIR) idler in optical parametric generation may lead to more than 15-fold relative spectral narrowing of the generated MIR signal. Moreover, the SFG process may also lead to 6-fold signal coherence…
Polyacrylonitrile block copolymers for the preparation of a thin carbon coating around TiO2 nanorods for advanced lithium-ion batteries.
2013
Herein, a new method for the realization of a thin and homogenous carbonaceous particle coating, made by carbonizing RAFT polymerization derived block copolymers anchored on anatase TiO2 nanorods, is presented. These block copolymers consist of a short anchor block (based on dopamine) and a long, easily graphitizable block of polyacrylonitrile. The grafting of such block copolymers to TiO2 nanorods creates a polymer shell, which can be visualized by atomic force microscopy (AFM). Thermal treatment at 700 °C converts the polyacrylonitrile block to partially graphitic structures (as determined by Raman spectroscopy), establishing a thin carbon coating (as determined by transmission electron m…
Stabilizing nanostructured lithium insertion materials via organic hybridization: A step forward towards high-power batteries
2014
Abstract Herein, we present the electrochemical characterization of carbon-coated TiO 2 nanorods, obtained by carbonizing RAFT (reversible addition fragmentation chain transfer) polymerization derived block copolymers anchored on anatase TiO 2 nanorods. These carbon-coated TiO 2 nanorods show an improved electrochemical performance in terms of first cycle reversibility, specific capacity, cycling stability, and high rate capability. More importantly, however, the structural disordering observed in the uncoated TiO 2 nanorods by means of galvanostatic and potentiodynamic cycling as well as ex situ XRD analysis, does not occur for the carbon-coated material. Preventing this structural disorde…