7784-21-6Relevant articles and documents
Catalytic synthesis of aluminum hydride in the presence of palladium black
Normatov
, p. 558 - 560 (2004)
The catalytic properties of a palladium catalyst in the formation of aluminum hydride are studied. The formation of stoichiometric aluminum hydride is determined by XRD, DTA, and spectrophotometry. Findings are rationalized in terms of the electron-chemical catalytic scheme.
Powerful Surface Chemistry Approach for the Grafting of Alkyl Multilayers on Aluminum Nanoparticles
Fogliazza, Morgan,Sicard, Lorette,Decorse, Philippe,Chevillot-Biraud, Alexandre,Mangeney, Claire,Pinson, Jean
, p. 6092 - 6098 (2015)
The synthesis of aluminum nanoparticles (Alnp) has raised promising perspectives these past few years for applications in energetic materials. However, because of their high reactivity, it is crucial to functionalize them before their use. In this work, we propose an original and simple chemical approach to graft spontaneously alkyl layers derived from alkyl halides at the surface of Alnp, by relying on the highly reductive character of these nanoparticles, when they are in the unoxidized form. Alnp were prepared in a glovebox and reacted with alkyl halides (RI and RBr) to give modified Alnp-R, as shown by infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction, thermogravimetric analysis (TGA), and microscopy. The coating is made of alkyl multilayers, which were found to be strongly anchored at the Alnp surface, as it resisted 2 h of rinsing in toluene. An electrocatalytic electron transfer promoted by Alnp is proposed to describe the mechanism of this grafting reaction.
Surface changes on AlH3 during the hydrogen desorption
Kato, Shunsuke,Bielmann, Michael,Ikeda, Kazutaka,Orimo, Shin-Ichi,Borgschulte, Andreas,Zuettel, Andreas
, (2010)
Surface change of α -AlH3 during the hydrogen desorption was investigated by means of in situ x-ray photoelectron spectroscopy combined with thermal desorption spectroscopy. The surface of AlH3 covered by an oxide layer significantly changes upon hydrogen desorption and the hydrogen desorption rate increases remarkably. In this study, the role of the surface oxide layer on AlH3 in view of the hydrogen desorption kinetics was investigated. AlH3 only decomposes into Al and H2 at the free surface and not in the bulk. Therefore, a closed surface oxide layer prevents the thermodynamically unstable AlH3 from decomposition.
METHYLIDYNE TRICOBALT NONACARBONYL CLUSTERS; OPTICALLY ACTIVE SILICON AND GERMANIUM DERIVATIVES, AND SUBSTITUTIONS AT SILICON
Combes, Christian E. J.,Corriu, Robert J. P.,Henner, Bernard J. L.
, p. 257 - 270 (1981)
The preparation and alcoholysis of chiral chlorosilanes containing the noncarbonyltricobaltcarbon cluster, RR'Si(Cl)CCo3(CO)9, is described.The alkoxy derivatives react with i-Bu2AlH or BF3*Et2O to give the corresponding silicon hydride or fluoride.Reacti
Aluminium hydride: A reversible material for hydrogen storage
Zidan, Ragaiy,Garcia-Diaz, Brenda L.,Fewox, Christopher S.,Stowe, Ashley C.,Gray, Joshua R.,Harter, Andrew G.
, p. 3717 - 3719 (2009)
Aluminium hydride has been synthesized electrochemically, providing a synthetic route which closes a reversible cycle for regeneration of the material and bypasses expensive thermodynamic costs which have precluded AlH3 from being considered as
A Universally Applicable Methodology for the Gram-Scale Synthesis of Primary, Secondary, and Tertiary Phosphines
Rinehart, N. Ian,Kendall, Alexander J.,Tyler, David R.
supporting information, p. 182 - 190 (2018/02/06)
Although organophosphine syntheses have been known for the better part of a century, the synthesis of phosphines still represents an arduous task for even veteran synthetic chemists. Phosphines as a class of compounds vary greatly in their air sensitivity, and the misconception that it is trivial or even easy for a novice chemist to attempt a seemingly straightforward synthesis can have disastrous results. To simplify the task, we have previously developed a methodology that uses benchtop intermediates to access a wide variety of phosphine oxides (an immediate precursor to phosphines). This synthetic approach saves the air-free handling until the last step (reduction to and isolation of the phosphine). Presented herein is a complete general procedure for the facile reduction of phosphonates, phosphinates, and phosphine oxides to primary, secondary, and tertiary phosphines using aluminum hydride reducing agents. The electrophilic reducing agents (iBu)2AlH and AlH3 were determined to be vastly superior to LiAlH4 for reduction selectivity and reactivity. Notably, it was determined that AlH3 is capable of reducing the exceptionally resistant tricyclohexylphosphine oxide, even though LiAlH4 and (iBu)2AlH were not. Using this new procedure, gram-scale reactions to synthesize a representative range of primary, secondary, and tertiary phosphines (including volatile phosphines) were achieved reproducibly with excellent yields and unmatched purity without the need for a purification step.
Oxazolidines as Intermediates in the Asymmetric Synthesis of 3-Substituted and 1,3-Disubstituted Tetrahydroisoquinolines
Raghavan, Sadagopan,Senapati, Puspamitra
, p. 6201 - 6210 (2016/08/16)
A diastereoselective mercury(II)-promoted intramolecular cyclization of unsaturated aldehyde via an oxazolidine to prepare C-3-substituted tetrahydroisoquinoline is disclosed. The C-3 stereogenic center is subsequently exploited to create the C-1 stereocenter by coordination of the nucleophilic reagent to the oxygen atom of oxazolidine. Both cis- and trans-1,3-disubstituted tetrahydroisoquinolines can be readily prepared. In addition, when a cationic rhodium complex was used, intramolecular hydroamination was effected, thus avoiding mercury(II) salts and demercuration. The reaction is general and works well using aliphatic and aromatic aldehydes.
Synthesis and pharmacological evaluation of conformationally restricted κ-opioid receptor agonists
Wenker, Yvonne,Soeberdt, Michael,Daniliuc, Constantin,St?nder, Sonja,Schepmann, Dirk,Wünsch, Bernhard
, p. 2368 - 2380 (2016/12/18)
In order to obtain novel polar κ agonists the κ-pharmacophoric ethylenediamine structural element was embedded in a rigid bicyclic scaffold. The pyridooxazine system was selected since it contains polar O- and N-atoms in the 1- and 7-positions, respectively. An axially oriented pyrrolidine ring was attached at the 5-position and the dichlorophenylacetyl moiety was introduced at N-4. The key steps of the 11-step synthesis are a double Henry reaction of iminodiacetaldehyde 7 with nitromethane and the introduction of the azido moiety of 13 by Mitsunobu reaction of the alcohol 11 with Zn(N3)2·(pyridine)2. The X-ray crystal structure analysis of 17b shows a dihedral angle N(acyl)-C-C-N(pyrrolidine) of ?60.8(2)°, which is close to the postulated optimal angle. Moderate κ affinity was found for the secondary amine 17a (Ki = 132 nM) and the methyl derivative 17b (Ki = 266 nM). In the [35S]GTPγS assay the secondary amine 17a showed 28% agonistic activity compared to U-69,593. Although 17a and 17b contain all crucial κ-pharmacophoric elements, their κ affinity is rather low, which might be attributed to the unfavorable cis-orientation of the pyrrolidine ring and the dichlorophenylacetamido moiety and/or the additional O- and N-atoms in the 1- and 7-positions.
Hydrogen release reactions of Al-based complex hydrides enhanced by vibrational dynamics and valences of metal cations
Sato,Ramirez-Cuesta,Daemen,Cheng,Tomiyasu,Takagi,Orimo
supporting information, p. 11807 - 11810 (2016/10/09)
Hydrogen release from Al-based complex hydrides composed of metal cation(s) and [AlH4]- was investigated using inelastic neutron scattering viewed from vibrational dynamics. The hydrogen release followed the softening of translational and [AlH4]- librational modes, which was enhanced by vibrational dynamics and the valence(s) of the metal cation(s).
An unexpected pentacarbonyl chromium complexation of a cyano group of the ABC core of cephalotaxine
Quteishat, Laith,Panossian, Armen,Le Bideau, Franck,Alsalim, Rana,Retailleau, Pascal,Troufflard, Claire,Rose, Eric,Dumas, Fran?oise
, p. 35 - 42 (2015/01/09)
A new penta-carbonyl chromium(0) complex of the type [Cr(CO)5(L)] (L = tetracyclic pyrrolobenzazepine unit 3) was surprisingly obtained by reacting [Cr(CO)3(naphthalene)] or [Cr(CO)3(tmtach)] with the tetracyclic pyrrolobenzazepine unit 3 in octane-ether/THF-solvent mixtures or acetone under ambient temperature or reflux. The new complex 13 has been characterized by spectral analysis including IR, 1H and 13C NMR data. For comparison purposes, the safrole-tricarbonyl chromium(0) complex 12 was prepared and characterized. X-ray diffraction analyses of both complexes were determined. Based on the above data, an octahedral structure has been assigned to the new complex 13.
