Search results for "Hydride"
showing 10 items of 322 documents
Efficient and Mild Ytterbium(III)-Catalyzed Tosylation of Alcohols.
2004
Ytterbium(III) trifluoromethanesulfonate efficiently catalyzes the reaction of primary and secondary alcohols with toluenesulfonic acid anhydride to yield the alkyl tosylates in high yields. The reactions were carried outunder neutral and mild conditions and product purification was easily achieved by means of short column chromatography.
Critical review of the atomic spectrometric analysis of arsenic in foods
1994
The literature on the determination of arsenic in foods by atomic spectroscopy involving hydride generation, platform furnace Zeeman and inductively coupled plasma has been critically reviewed. Hydride generation has been largely displaced as a powerful tool by platform furnace Zeeman, using the STPF (stabilized temperature platform furnace) concept for the control of interferences. Inductively coupled plasma with conventional pneumatic nebulization has been little used. An alternative is to employ hydride generation-ICP with extraction of the arsenic in an organic phase. This technique permits proper control of interferences together with an increase in sensitivity. Depending on the conten…
Structural and hydrogenation study on the ball milled TiH2–Mg–Ni
2015
International audience; With the aim of further understanding for TieNieMg alloys and their hydrogenation behavior, powders of TiH2, Mg and Ni with the molar ratio of 3:1:2 have been mechanically milled for 10 h, 20 h, 30 h, 40 h according to the stoichiometry (TiH2)1.5Mg0.5Ni. Microstructures of the milled sample were analyzed and their hydrogenation properties as negative electrodes for Ni-MH batteries were studied. Phase change with milling time revealed the fast formation of the Ti-Mg-H FCC phase. The alloying priority among Ti, Mg and Ni was demonstrated by comparing phase compositions in different milling time. Hydrogen capacities evaluated by both solidegas reaction and electrochemic…
Free and bound hydroxyl and carboxyl groups in the cutin of Quercus suber leaves
1984
Abstract The number of free and bound hydroxyl and carboxyl groups of the cutin of Quercus suber leaves was investigated by the lithium borohydride hydrogenolysis of mesyl-cutin compared with the lithium borohydride hydrogenolysis of untreated cutin. Fifty per cent of the vic -diol groups of the trihydroxy C 18 acid component and twenty five per cent of the secondary hydroxyl groups of the dihydroxy C 16 acid component are free. The rest of the secondary and all of the primary hydroxyl groups are esterified; all carboxyl groups are esterified.
On Transition Structures for Hydride Transfer Step: A Theoretical Study of the Reaction Catalyzed by Dihydrofolate Reductase Enzyme
1996
Abstract A theoretical study is presented of the catalytic mechanism of dihydrofolate reductase (DHFR) enzyme based upon the characterization of the transition structure (TS) for the hydride transfer step. Analytical gradients at AM1 and PM3 semiempirical levels have been used to characterize the saddle point of index one (SPi-1) on global energy hypersurface for the hydride transfer in the active site of DHFR enzyme. The geometry, stereochemistry, electronic structure, and transition vector (TV) components associated to SPi-1 are qualitatively computational level independent. The TV amplitudes show primary and secondary isotope effects to be strongly coupled. The geometrical arrangement of…
Computational Modeling of Biological Systems: The LDH Story
2010
Lactate dehydrogenases, LDH, catalyzed reaction has been used in this chapter as a conductor wire to present the evolution and difficulties on computing methods to model chemical reactions in enzymes, since the early calculations based at semiempirical level carried out in gas phase to the recent sophisticated simulations based on hybrid Quantum Mechanical/Molecular Mechanics Dynamics (QM/MM MD) schemes. LDH catalyzes the reversible transformation of pyruvate into lactate. The chemical step consists in a hydride and a proton transfer from the cofactor (NADH) and a protonated histidine (His195), respectively. This fact has generated a lot of controversy about the timing of both transfers in …
Reductions of M{N(SiMe3)2}3 (M = V, Cr, Fe): Terminal and Bridging Low-Valent First-Row Transition Metal Hydrido Complexes and “Metallo-Transaminatio…
2021
The reaction of the vanadium(III) tris(silylamide) V{N(SiMe3)2}3 with LiAlH4 in diethyl ether gives the highly unstable mixed-metal polyhydride [V(μ2-H)6[Al{N(SiMe3)2}2]3][Li(OEt2)3] (1), which was structurally characterized. Alternatively, performing the same reaction in the presence of 12-crown-4 affords a rare example of a structurally verified vanadium terminal hydride complex, [VH{N(SiMe3)2}3][Li(12-crown-4)2] (2). The corresponding deuteride 2D was also prepared using LiAlD4. In contrast, no hydride complexes were isolated by reaction of M{N(SiMe3)2}3 (M = Cr, Fe) with LiAlH4 and 12-crown-4. Instead, these reactions afforded the anionic metal(II) complexes [M{N(SiMe3)2}3][Li(12-crown-…
The mechanism of formation of 3H,9H-Pyrano[3,4-b]indol-3-ones from 3-indolalkanoic acids
1991
The mechanism of the formation of 1-methyl-3H,9H-pyrano[3,4-b]indol-3-one (4) from the corresponding 3-indolacetic acid 1 is discussed. The suggested mechanism is substantiated by the isolation of a stable intermediate 2 and its transformations in the presence of acetic anhydride and/or Lewis acids.
Mixed Dialkylaluminum Chlorides and Mixed Trimethylorganoaluminates in Chemoselective 1,4 Addition Reactions to Alkylidene Malonic Acid Diethyl Ester
2000
Mixed alkyl-methyl- and aryl-methylorganoaluminum chlorides 6 were formed by reaction of methylaluminum dichloride with organolithium or Grignard compounds and used for chemoselective 1,4 addition of higher alkyl, aryl, alkenyl and alkinyl groups to alkylidine malonic esters 1 and 2. As an alternative, mixed trimethylorganoaluminates 7 can also be applied for these Michael addition reactions. For conjugate addition of alkenyl groups to alkylidene malonates 1 and 2, alkenyl diisopropylalanes 10 obtained from alkynes and diisopropylaluminum hydride proved the most efficient reagents. Using these novel mixed organoaluminum compounds, β-branched malonic (carboxylic) acid derivatives 3c, 8, 9 an…
Characterization of β-B-Agostic Isomers in Zirconocene Amidoborane Complexes
2009
The reaction of Cp(x)(2)ZrCl(2) (Cp(x) = Cp, Cp*) with ammonia borane in presence of n-butyllithium yielded Cp(2)Zr(Cl)NH(2)BH(3) and Cp(x)(2)Zr(H)NH(2)BH(3). These derivatives are isoelectronic with the ethyl zirconocene chloride and hydride, respectively, and feature a chelating amidoborane ligand coordinating through a Zr-N bond and a Zr-H-B bridge. In solution, each of the complexes consists of an equilibrium mixture of two isomers differing in the orientation of the amidoborane ligand with respect to the Zr-X bond (X = H, Cl), while in the solid state, only one isomer was observed. Such isomers have not been characterized for any metal complexes containing the isoelectronic beta-agosti…