Search results for "hydride"
showing 10 items of 322 documents
Tetracarbonyltungsten(0)-bis(μ-dimethylphosphido)-bis[dicyclopentadienylhydridomolybdenum(IV)]
2002
The title trinuclear WMo2 compound, [Mo2WH2(C5H5)4(C2H6P)2(CO)4], was obtained by opening of the hydride bridge in the dinuclear dibridged (μ-PMe2,H){(C5H5)2Mo}{W(CO)4} complex (MoIV) upon the action of (C5H5)2Mo(PMe2H) (MoII) in THF solution. This involves the formal conversion of MoII to MoIV.
Yttrium Hydrido Complexes that Contain a Less “Constrained Geometry” Ligand: Synthesis, Structure, and Efficient Hydrosilylation Catalysis
2001
σ-Bond metathesis of the new linked amino-cyclopentadiene (C5Me4H)CH2SiMe2NHCMe3 with Y(CH2SiMe3)3(THF)2 gave the alkyl-yttrium complex [Y(η5:η1-C5Me4CH2SiMe2NCMe3)(CH2SiMe3)(THF)] (1) in 66% yield. Compound 1 was characterized by NMR spectroscopy and X-ray crystal structure analysis. By hydrogenolysis, 1 was quantitatively converted into the dimeric hydride [Y(η5:η1-C5Me4CH2SiMe2NCMe3)(THF)(μ-H)]2 (2). X-ray crystal structure analysis revealed a Y2H2 core connected to two [Y(η5:η1-C5Me4CH2SiMe2NCMe3)(THF)] fragments in a skewed manner, with a relatively long yttrium−yttrium distance of 3.7085(8) A. In solution, two diastereomers were observed by 1H NMR spectroscopy at −78 °C. Dimer 2 was s…
High yield synthesis of trinuclear [M3S4X3(diphos)3]+ (M=Mo, W; X=Cl, Br and diphos=dmpe, dppe) molecular clusters from solid state materials. Synthe…
2001
The excision of polymeric {M 3 S 7 X 4 } x (M=Mo, W; X=Cl, Br) cluster phases with diphosphines (dmpe, dppe) in acetonitrile affords a one step general synthetic route for the preparation of trinuclear molecular clusters with formula [M 3 S 4 X 3 (diphos) 3 ] + (M=Mo, W; X=Cl, Br and diphos=dmpe, dppe) in high yields. Following this strategy, the cluster cations [Mo 3 S 4 Br 3 (dmpe) 3 ] + and [W 3 S 4 Br 3 (dppe) 3 ] + have been prepared for the first time. This last tungsten cluster has proved to be a useful synthon for the synthesis of the hydride derivative [W 3 S 4 H 3 (dppe) 3 ] + in moderate yields. The crystal structure of [W 3 S 4 H 3 (dppe) 3 ](BPh 4 ) consists of a equilateral tu…
On-line vapor-phase generation combined with Fourier transform infrared spectrometry
2008
We present a critical review of on-line vapor-phase generation combined with Fourier transform infrared spectrometry for detection. We discuss different experimental approaches developed for generating the vapor phase based on different principles (e.g., thermal volatilization, acid-base, redox reaction and covalent hydride generation). Using examples of applications, we try to demonstrate the analytical potential of on-line vapor-phase generation in vibrational spectrometry in order to improve the selectivity and the sensitivity of the measurement step and to make environmentally-friendly procedures available for problem solving in the analytical laboratory. We pay special attention to int…
Synthese von 2-Acyloxy- und 2-Alkyloxy-3-ketoglycalen und ihren Bromaddukten
1983
Die an den Hydroxygruppen acetyl-, pivaloyl- und methylgeschutzten 2-Hydroxy-3-ketoglycale 5a, 5b bzw. 11 werden durch Oxidation der entsprechenden 1-O-Acylglucopyranosen 3a, 3b bzw. 9 an der freien 3-Hydroxygruppe mit Dimethylsulfoxid/Acetanhydrid oder Chlorsulfonylisocyanat hergestellt und charakterisiert. Nur beim Acetylderivat 3a verlaufen die Oxidation und die Eliminierung des 1-Acetyloxysubstituenten in einem Schritt. Beim Pivaloylderivat 3b und beim Methylderivat 9 mus die Eliminierung aus der 3-Ulose 4 bzw. 10 mit Diazabicycloundecen (DBU) vervollstandigt werden. – Die geschutzten Hex-1-enopyran-3-ulosen 5a, 5b und 11 addieren Brom stereoselektiv unter Bildung der D-ribo-konfigurier…
Lipid hydroperoxides determination in milk‐based infant formulae by gas chromatography
2003
A simple gas chromatograph using a flame ionization detector and a polar capillary column method is proposed for determining hydroperoxides in the lipid fraction of milkbased infant formulas. Tricosanoic acid is used as internal standard. The method includes the following steps: a) the extraction of fat with chloroform/methanol (2:1, v/v), b) the reduction of hydroperoxide acids to hydroxide acids with hydrogen gas and palladium as a catalyst, c) the transmethylation to obtain the methyl esters with acetyl chloride and methanol/ hexane (4:1, v/v), and d) an acetylation with acetic anhydride/ pyridine (4:1, v/v) to obtain an acetoxy derivate of the hydroxide present. Two chromatography runs,…
Rapid and simultaneous high-performance liquid chromatography assay of polyamines and monoacetylpolyamines in biological specimens
2000
A rapid, resolutive and reproducible reversed-phase high-performance liquid chromatography (RP-HPLC) method was developed for polyamines and acetylpolyamines by adopting pre-column derivatization with benzoyl chloride. In a single run lasting less than 15 min ten polyamines were separated as well as traces of benzoic acid, methylbenzoate and benzoic anhydride. These contaminants, produced during the derivatization reaction, were almost all eliminated by washing steps envisaged in the same procedure. This simple and sensitive method can be applied to routine determination of polyamines in biological samples. A fine application of this procedure to the determination of endogenous content of p…
Description of hysteresis of Nickel Metal Hydride Battery
2012
A Dynamic Preisach Model for the description of the hysteresis in Nickel Metal Hydride Battery is presented. Both the hysteresis and the dynamical features of charging and discharging cycles are described. The identification of the model is obtained by using a neural network technique developed for magnetic systems. The model is validated by some experimental tests on commercial batteries.
A Two-State Computational Investigation of Methane C-H and Ethane C-C Oxidative Addition to [CpM(PH3)]n+ (M=Co, Rh, Ir;n=0, 1)
2006
Reductive elimination of methane from methyl hydride half-sandwich phosphane complexes of the Group 9 metals has been investigated by DFT calculations on the model system [CpM(PH(3))(CH(3))(H)] (M = Co, Rh, Ir). For each metal, the unsaturated product has a triplet ground state; thus, spin crossover occurs during the reaction. All relevant stationary points on the two potential energy surfaces (PES) and the minimum energy crossing point (MECP) were optimized. Spin crossover occurs very near the sigma-CH(4) complex local minimum for the Co system, whereas the heavier Rh and Ir systems remain in the singlet state until the CH(4) molecule is almost completely expelled from the metal coordinati…
Investigation into the reactivity of oxoniobocene complexes [Cp*2Nb(O)R] (Cp*=η5-C5Me5; R=H, OH, OMe) towards heterocumulenes: formation of carbamat…
2001
Abstract The reaction of [Cp*2NbCl2] (Cp*=η5-C5Me5) with KOH or Ba(OH)2·8H2O in THF was investigated under slightly modified conditions. In addition to the known complex [Cp*2Nb(O)H] (1), the new compound [Cp*2Nb(O)OH] (2) was formed. The reaction of 2 with PhNCS gave yellow [Cp*2Nb(O){SC(O)NHPh}] (3), while PhNCO formed yellow [Cp*2Nb(O){OC(O)NHPh}] (4). Complexes 3 and 4 were analytically and spectroscopically characterized. X-ray diffraction analyses of both compounds show that they contain either η1-S-thiocarbamato (3) or η1-O-carbamato ligand (4) along with a terminal NbO group. The reaction of 1 with one equivalent of PhNCO mainly gave orange [Cp*2NbH{OC(O)NPh}] (5) along with so…