3332-08-9Relevant articles and documents
Synthesis, structure and theoretical studies of the hydrido inverse crown [K2Mg2(NiPr2)4(μ-H) 2·(toluene)2]: A rare example of a molecular magnesium hydride with a Mg-(μ-H)2-Mg double bridge
Andrikopoulos, Prokopis C.,Armstrong, David R.,Kennedy, Alan R.,Mulvey, Robert E.,O'Hara, Charles T.,Rowlings, Rene B.
, p. 3354 - 3362 (2003)
Reaction of benzylpotassium, n,s-dibutylmagnesium and diisopropylamine in boiling toluene produces a rare example of a molecular magnesium hydride with a Mg-(μ-H)2-Mg double bridge, in [K2Mg 2(NiPr2)4(μ-H)2· (toluene)2] (1). In an effort to rationalise the formation of 1, a series of DFT calculations were performed. This report of 1 establishes the first isostructural pair of Na and K complexes solvated by toluene to be reported in the Cambridge Crystallographic Database. In comparison with its previously reported Na analogue, 2, the metal-arene centroid distances are considerably shorter (by 0.159 A) in the new complex reported here. It was found that a hydrocarbon solution of 1 is capable of reducing benzophenone to benzhydrol in moderate yields (74%). ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).
Catalytic conversion of glycerol to allyl alcohol; Effect of a sacrificial reductant on the product yield
Sanchez, Gizelle,Friggieri, Jarrod,Adesina, Adesoji A.,Dlugogorski, Bogdan Z.,Kennedy, Eric M.,Stockenhuber, Michael
, p. 3090 - 3098 (2014/08/18)
A continuous process for the conversion of glycerol to allyl alcohol, where ammonia or organic acids are added to the feed as sacrificial reductants, was investigated. Significant enhancement on the rate of formation and yield of the allyl alcohol is observed with some of the reducing agents examined over an alumina-supported iron catalyst. Optimising the molar ratio of the reductant relative to feed glycerol results in an increase in the yield of allyl alcohol from 9% (in the absence of additives) to 11.3% with ammonia, 15.1% with ammonium hydroxide, 17.8% with oxalic acid and 19.5% with formic acid. Moreover, the addition of other organic acids, which are produced in a typical glycerol conversion experiment, was studied. However, acetic and propanoic acids had little effect on the rate of formation of allyl alcohol. Analysis of the product distribution in the liquid and gas phases when oxalic and formic acids were added suggests a two-step process for the formation of allyl alcohol under the operating conditions of the reaction; the initial step involves the dehydration of glycerol while the second comprises the reduction of the species produced in step one. the Partner Organisations 2014.
Structures of Sterically Overcrowded and Charge-Perturbated Molecules, 51. - Oxidative Decomposition of Tetraisopropyltetrazene: Isolation and Single-Crystal Structures of the Radical Cation Salt (SbCl6(-)) and of the N2 Elimination Product ...
Bock, Hans,Goebel, Ilka,Naether, Christian,Solouki, Bahman,John, Andreas
, p. 2197 - 2208 (2007/10/02)
The single-electron oxidation of tetraisopropyltetrazene by the advantageous, oxygen-free SbCl5/H2CCl2 redox system yields dark-red crystals of tetraisopropyltetrazenium hexachloroantimonate.Their structure determination at temperatures of 100, 200, and 293 K, the first one of a 2-tetrazene radical cation, proves a planar skeleton C2N-N=N-NC2(.+) with nearly identical NN bond lengths.The reaction of tetraisopropyltetrazene with surplus SbCl5 yields the N2 elimination product isopropylisopropylideneammonium haxachloroantimonate, which also has been crystallized and structurally characterized.Due to the conformation of the C3 subunits perpendicular to each other, the cation (H3C)2HC-HN(+)=C(CH3)2 is extremely overcrowded as demonstrated by an angle CNC of 129 deg.In addition, the thermal decomposition of tetraisopropyltetrazene in the gasphase has been analyzed PE-spectroscopically, its first and second oxidation potentials have been determined cyclovoltammetrically, and the ESR signal pattern of its radical in solution has been recorded and assigned.Based on the experimental data, a possible pathway for the oxidative decomposition of the title compound is discussed. - Key Words: Tetrazene, tetraalkyl-, oxidation / Photoelectron spectra / ESR spectra / Calculations, AM1
