Chemoselective reduction of azides catalyzed by molybdenum xanthate by using phenylsilane as the hydride source

A chemoselective, neutral, and efficient strategy for the reduction of azides to corresponding amines catalyzed by dioxobis(N,N,-diethyldithiocarbamato) molybdenum complex (1, MoO2[S2CNEt2](2)) in the presence of phenylsilane is discovered. This chemoselective reduction strategy tolerates a variety of reducible functional groups.

High lithium storage in micrometre sized mesoporous spherical self-assembly of anatase titania nanospheres and carbon

Composite of anatase titania (TiO2) nanospheres and carbon grown and self-assembled into micron-sized mesoporous spheres via a solvothermal synthesis route are discussed here in the context of rechargeable lithium-ion battery. The morphology and carbon content and hence the electrochemical performance are observed to be significantly influenced by the synthesis parameters. Synthesis conditions resulting in a mesoporous arrangement of an optimized amount carbon and TiO2 exhibited the best lithium battery performance. The first discharge cycle capacity of carbon-titania mesoporous spheres (solvothermal reaction at 150 degrees C at 6 h, calcination at 500 degrees C under air, BET surface area 80 m(2)g(-1)) was 334 mAhg(-1) (approximately 1 Li) at current rate of 0.066 Ag-1. High storage capacity and good cyclability is attributed to the nanostructuring of TiO2 (mesoporosity) as well as due to formation of a percolation network of carbon around the TiO2 nanoparticles. The micron-sized mesoporous spheres of carbon-titania composite nanoparticles also show good rate cyclability in the range (0.066-6.67) Ag-1.

Synthesis and structural characterization of a new ruthenium hydride ethylene complex

A ruthenium(II) ethylene complex, trans-[Ru(H)(C2H4)- (dppm)(2)][BF4], hearing two 1,1-bis(diphenylphosphino) methane (dppm) ligands has been synthesized and structurally characterized using X-ray crystallography. In the molecular structure, the Ru-II center shows a distorted octahedral coordination geometry formed by four P atoms of the two chelating dppm ligands, a hydride, and an ethylene ligands. The four dppm P atoms are almost co-planar with the hydride and the ethylene ligands perpendicular to this plane. The C-C bond distance of the bound ethylene is 1.375(6) angstrom, which is elongated by 0.042 angstrom as compared to free ethylene (1.333(2) angstrom). The packing diagram of the complex shows two voids or channels, which are occupied by BF4- counterion and water molecules.

Organometallic chemistry of diphosphazanes. Part 26. Ruthenium hydride complexes of chiral and achiral diphosphazane ligands and asymmetric transfer hydrogenation reactions

The half-sandwhich ruthenium chloro complexes bearing chelated diphosphazane ligands, [(eta(5)-Cp)RuCl{kappa(2)-P,P-(RO)(2)PN(Me)P(OR)(2)}] [R = C6H3Me2-2,6] (1) and [(eta(5)-Cp*)RuCl{kappa(2)-P, P-X2PN(R)PYY'}] [R = Me, X = Y = Y' = OC6H5 (2); R = CHMe2, X-2 = C20H12O2, Y = Y' = OC6H5 (3) or OC6H4'Bu-4 (4)] have been prepared by the reaction of CpRu(PPh3)(2)Cl with (RO)(2)PN(Me)P(OR)(2) [R = C6H3Me2-2,6 (L-1)] or by the reaction of [Cp*RuCl2](n) with X2PN(R)PYY' in the presence of zinc dust. Among the four diastereomers (two enantiomeric pairs) possible for the "chiral at metal" complexes 3 and 4, only two diastereomers (one enantiomeric pair) are formed in these reactions. The complexes 1, 2, 4 and [(eta(5)-Cp)RuCl {kappa(2)-P,P-Ph2PN((S)-*CHMePh)PPhY)] [Y = Ph (5) or N2C3HMe2-3,5 (SCSPRRu)-(6)] react with NaOMe to give the corresponding hydride complexes [(eta(5) -Cp)RuH {kappa(2)-P,P-(RO)(2)PN(Me)P(OR)(2)}] (7), [(eta(5)-Cp*)RuH {kappa(2)-P,P'-X2PN(R)PY2)] [R = Me, X = Y = OC6H5 (8); R = CHMe2, X-2 = C20H12O2, Y = OC6H4'Bu-4 (9)] and [(eta(5) -Cp)RuH(kappa(2)-P, P-Ph2PN((S)-*CHMePh)PPhY)][Y =Ph (10) or N2C3HMe2-3,5 (SCSPRRu)(11a) and (SCSPSRu)-(11b)]. Only one enantiomeric pair of the hydride 9 is obtained from the chloro precursor 4 that bears sterically bulky substituents at the phosphorus centers. On the other hand, the optically pure trichiral complex 6 that bears sterically less bulky substituents at the phosphorus gives a mixture of two diastereomers (11a and 11b). Protonation of complex 7 using different acids (HX) gives a mixture of [(eta(5)- Cp)Ru(eta(2)-H-2){kappa(2)-P, P-(RO)(2)PN(Me)P(OR)(2))]X (12a) and [(eta(5)-Cp)Ru(H)(2){kappa(2)-P, P-(RO)(2)PN(Me)P(OR)(2)}]X (12b) of which 12a is the major product independent of the acid used; the dihydrogen nature of 12a is established by T, measurements and also by synthesizing the deuteride analogue 7-D followed by protonation to obtain the D-H isotopomer. Preliminary investigations on asymmetric transfer hydrogenation of 2-acetonaphthone in the presence of a series of chiral diphosphazane ligands show that diphosphazanes in which the phosphorus centers are strong pi-acceptor in character and bear sterically bulky substituents impart moderate levels of enantioselectivity. Attempts to identify the hydride intermediate involved in the asymmetric transfer hydrogenation by a model reaction suggests that a complex of the type, [Ru(H)(Cl){kappa(2)-P,P-X2PN(R)PY2)(solvent)(2)] could be the active species in this transformation. (c) 2007 Elsevier B.V. All rights reserved.

Elastic properties of fast ion conducting lithium based borate glasses

Elastic properties of Li2O-PbO-B2O3 glasses have been investigated using sound velocity measurements at 10 MHz. Four series of glasses have been investigated with different concentrations of Li2O, PbO and B2O3. The variations of molar volume have been examined for the influences of Li2O and PbO. The elastic moduli reveal trends in their compositional dependence. The bulk and shear modulus increases monotonically with increase in the concentration of tetrahedral boron which increases network dimensionality. The variation of bulk moduli has also been correlated to the variation in energy densities. The Poisson's ratio found to be insensitive to the concentration of tetrahedral boron in the structure. The experimental Debye temperatures are in good agreement with the expected theoretical values. Experimental observations have been examined in view, the presence of borate network and the possibility of non-negligible participation of lead in network formation. (c) 2005 Elsevier B.V. All rights reserved.

Infrared spectrum of ferroelectric lithium hydrazinium sulphate [Li (N2H5) SO4]

Dielectric observations on lithium hydrazinium sulphate have shown earlier that it is ferroelectric over a range of temperatures from below −15° C. to above 80° C. and a new type of hydrogen bond rearrangement which would allow the protons to migrate along the chain has also been suggested by others. The infrared spectrum of LiH z S in the form of mull and as single crystal sections parallel and perpendicular to the ‘C’ axis exhibit about 21 well-defined absorption maxima. The position and the width of the maxima agree with the known structure of the crystal according to which the hydrazine group exists in the form of the hydrazinium ion, NH2·NH3+ and the observed N+-H frequencies agree better with the new correlation curve given by R. S. Krishnan and K. Krishnan (1964). However it has been pointed out that from a comparative study of the new infrared spectra of hydrazonium sulphate and lithium ammonium sulphate that the absorption band at 969 cm.−1 is due to N-N stretching vibration and that the fairly intense band between 2050–2170 cm.−1 is due to the bending vibrations of the NH3+ group.

Raman spectra of ferro-electric crystals Part IV. Lithium hydrazinium sulphate (LiN2H5SO4)

The Raman spectrum of lithium hydrazinium sulphate has been recorded both in the single crystal form and in aqueous solutions. The crystal exhibits thirty-eight Raman lines having the frequency shifts 52, 70, 104, 146, 174, 220, 260, 302, 350, 454, 470, 610, 630, 715, 977, 1094, 1115, 1132, 1177, 1191, 1260, 1444, 1493, 1577, 1630, 1670, 2205, 2484, 2553, 2655, 2734, 2848, 2894, 2939, 3028, 3132, 3290 and 3330 cm.−1 The aqueous solution gave rise to six Raman lines at 452, 980, 1050–1200, 1260, 1425 and 1570 cm.−1 apart from a maximum at 180 cm.−1 in the ‘wing’ accompanying the Rayleigh line. The observed Raman lines have been assigned as arising from the vibrations of the SO4 ion, N2H5+ ion, Li-O4 group, hydrogen bond and the lattice. The influence of the hydrogen bond on the N-H stretching vibrations has been pointed out. The various features of the observed spectrum strongly support the hypothesis that the NH3 group in the crystal is rotating around the N-N axis at room temperature.

Preparation of lithium amalgam

Lithium amalgam is useful in effecting Wurtz type intramolecular and intermolecular coupling reactions.

Synthetic investigations in the sesamin group - Part I. Synthesis of samin, a degradation product of sesamolin

Ethylα-bromovinylacetate (VII) was condensed with the sodio derivative of ethyl piperonoylacetate (VIII) to give diethylα-vinyl-α′-piperonoylsuccinate (IX). The latter on reduction with lithium aluminium hydride furnished the triol (X), which underwent smooth cyclisation with 1% ethanolic hydrogen chloride to 2-(3′, -methylenedioxyphenyl)-hydroxymethyl-4-vinyltetrahydrofuran (XIa). The structure of XIa was established by Oppenauer oxidation to an aldehyde. Ozonolysis of XIa afforded samin (I).

Steroids and related natural products. VIII. Synthesis of oxasteroids

Peroxydisulfuric acid oxidation of testosterone propionate, progesterone, and cholest-4-en-3-one has been shown to yield 3-oxo-17β-hydroxy-4-oxa-5α-androstane (I, after saponification), 3,20-dioxo-4-oxa-5α-pregnane (V) and 3-oxo-4-oxa-5α-cholestane (VII) respectively. Boron trifluoride etherate-lithium aluminum hydride reduction of δ-lactones I, V, and VII led to the corresponding tetrahydropyran derivatives (IIb, VIa, and VIII). Similar reduction of 3β-hydroxy-17-oxo-17a-oxa-D-homo-5α-androstane (XI) gave 3β-hydroxy-17a-oxa-D-homo-5α-androstane (XIIa). Diborane-boron trifluoride etherate was also found to reduce lactones to cyclic ethers, while reduction with diborane gave hemiacetals. Evidence in support of the structures and stereochemistry assigned to the lactones and their unusual reduction products has been summarized. A tentative mechanism is proposed for lactone → ether reduction employing diborane-boron trifluoride etherate.

The subsidence rates of suspensions of lithium stearate in n-heptane with n-alcohols as additives

Suspensions of lithium stearate in n-heptane are highly unstable, undergoing gelation even at concentrations as low as 1 g./1. The rate of subsidence of these weakly gelled suspensions is decreased at first by the addition of n-alcohols, but passes through a minimum in some cases. The minimum subsidence rate occurs while the adsorption of the alcohol is still below its saturation value. One possible explanation of the effect is that the solvent layer between particles at the junction points in the gel becomes simultaneously more polar, tending toward an increased gel strength, and also thicker, tending toward a decreased gel strength.

Potassium phosphate as a reagent for the gravimetric estimation of lithium

Previous attempts for the quantitative estimation of lithium as orthophosphate, employing an alkali metal phosphate, have not been successful. A method, is described for the estimation of lithium as trilithium phosphate from 60% ethyl alcohol solution at 65° to 70° C., employing potassium phosphate reagent, at pH 9.5. The method is applicable in the presence of varying amounts of sodium and/or potassium cations and chloride, sulfate, nitrate, and phosphate anions.

Selective para metalation of unprotected 3-methoxy and 3,5-dimethoxy benzoic acids with n-butyl lithium-potassium tert-butoxide (LIC-KOR): synthesis of 3,5-dimethoxy-4-methyl benzoic acid

The potassium salt of 3-methoxy and 3,5-dimethoxy benzoic acids undergoes deprotonation at the position para to the carboxylate group selectively when treated with LIC-KOR in THF at -78 degrees C and it has been extended to the synthesis of 3,5-dimethoxy-4-methyl benzoic acid. (C) 2000 Elsevier Science Ltd. All rights reserved.