593-51-1Relevant articles and documents
Nitrosyl Complexes of Molebdenum and Tungsten. Part 15. Iodo(monoalkylamido)nitrosylmolybdenum Complexes, some Related Tungten Compounds, and the Crystal and Molecular Structure of Ethylamido(iodo)nitrosylmolybdenum
McCleverty, Jon A.,Rae, A. Elizabeth,Wotochowicz, Iwona,Bailey, Neil A.,Smith, John M. A.
, p. 429 - 438 (1982)
The complexes (NO)I(Y)> (Y=NMe2 or NHR, where R=H, Me, Et, nPr, iPr, nBu, tBu, C6H11, C3H5, or CH2Ph) and (NO)Br(Y)> (Y=H, iPr, or CH2Ph) have been prepared by treatment of the species where Y=I(Mo) or Br(W) with ammonia primary amines, and NHMe2 respectively.Reaction of HB(3,5-Me2C3HN2)3>(NO)I(NH2)> with HCl, and with acetone in the presence of NEt3 respectively, gives (NO)Cl2> and Cl, and (NO)I(N=CMe2)>*Me2CO.The crystal and molecular structure of (NO)I(NHEt)>, as a di-isopropyl ether solvate, has been determined by X-ray diffraction methods using counter data and refined by block-diagonal least-squares procedures, to R=0.0534 for 3150 reflections.The molecule is six co-ordinate, with a linear Mo-N-O group, and a short Mo-NHEt bond.Crystals are monoclinic with a=40.00(3), b=12.751(10), c=10.60(3) angstroem.β=97.23(2) deg, space group P21/a, and Z=8.
Low-temperature photoluminescence spectroscopy of CH3NH3PbBrxCl3-x perovskite single crystals
Xu, Qiang,Shao, Wenyi,Zhang, Xinlei,Liu, Jun,Ouyang, Xiaoping,Tang, Xiaobin,Jia, Wenbao
, p. 185 - 190 (2019)
Organic-inorganic halide perovskite (OIHP) has attracted tremendous attention due to its potential applications in optoelectronics such as light emitting device and photodetector. Here, we have grown high quality CH3NH3PbBrx/su
Stereodynamics of Diethylmethylamine and Triethylamine
Bushweller, C. Hackett,Fleischman, Stephen H.,Grady, Gilbert L.,McGoff, Paul,Rithner, Christopher D.,et al.
, p. 6224 - 6236 (1982)
Diethylamine is the simplest acyclic trialkylamine that possesses the requisite symmetry that allows, in principle, the direct observation of both nitrogen inversion and isolated nitrogen-carbon bond rotation using 1H dynamic nuclear magnetic resonance (DNMR) spectroscopy.DNMR studies of diethylmethylamine and two deuterated derivatives complemented by empirical force-field calculations reveal a comprehensive picture of the stereodynamics of this representative acyclic trialkylamine.The DNMR studies show clear evidence for pyramidal inversion at nitrogen.In addition to nitrogen inversion, the results also speak for several "families" of rotamers for diethylmethylamine that undergo very rapid, DNMR-invisible intrafamily conformational exchange via isolated N-CH2 rotation while also undergoing higher barrier DNMR-visible interfamily exchange also via isolated N-CH2 rotation.The DNMR-visible N-CH2 rotation processes involve CCH3/N-alkyl eclipsing in the transition state while the DNMR-invisible processes involve CCH3/lone pair eclipsing.Although the symmetry of triethylamine precludes the DNMR-observation of nitrogen inversion, (1)H DNMR evidence for restricted N-CH2 rotation and empirical force-field calculations reveal stereodynamics for triethylamine that are highly analogous to diethylmethylamine.
Crystal Growth, Structural Phase Transitions, and Optical Gap Evolution of CH3NH3Pb(Br1-xClx)3 Perovskites
Alvarez-Galván,Alonso,López,López-Linares,Contreras,Lázaro,Fauth,Martínez-Huerta
, p. 918 - 924 (2019)
Chemically tuned inorganic-organic hybrid halide perovskites based on bromide and chloride anions CH3NH3Pb(Br1-xClx)3 have been crystallized and investigated by synchrotron X-ray diffraction (SXRD), scanning electron microscopy, and UV-vis spectroscopy. CH3NH3PbBr3 and CH3NH3PbCl3 experience successive phase transitions upon cooling, which are suppressed for intermediate compositions probably due to compositional disorder. For CH3NH3PbCl3, a transient phase, formerly described as tetragonal, was identified at 167.5 K; the analysis of SXRD data demonstrated that it is indeed orthorhombic, with space group Pnma, and a ≈ 2ap; b ≈ 2ap; c ≈ 2ap (ap is the ideal cubic perovskite unit-cell parameter). The band gap engineering brought about by the chemical management of CH3NH3Pb(Br1-xClx)3 perovskites can be controllably tuned: the gap progressively increases with the concentration of Cl ions from 2.2 to 2.9 eV, and shows a concomitant variation with the unit-cell parameters of the cubic phases at 295 K. This study provides an improved understanding of the structural and optical properties of the mixed CH3NH3Pb(Br1-xClx)3 perovskites.
Deoxygenation of primary amides to amines with pinacolborane catalyzed by Ca[N(SiMe3)2]2(THF)2
Gong, Mingliang,Guo, Chenjun,Jiang, Linhong,Luo, Yunjie,Yu, Chong
supporting information, p. 1201 - 1206 (2021/05/29)
Deoxygenative reduction of amides is a challenging but favorable synthetic method of accessing amines. In the presence of a catalytic amount of Ca[N(SiMe3)2]2(THF)2, pinacolborane (HBpin) could efficiently reduce a broad scope of amides, primary amides in particular, into corresponding amines. Functional groups and heteroatoms showed good tolerance in this process of transformation, and a plausible reaction mechanism was proposed.
Transition metal-free catalytic reduction of primary amides using an abnormal NHC based potassium complex: Integrating nucleophilicity with Lewis acidic activation
Bhunia, Mrinal,Sahoo, Sumeet Ranjan,Das, Arpan,Ahmed, Jasimuddin,Sreejyothi,Mandal, Swadhin K.
, p. 1848 - 1854 (2020/03/03)
An abnormal N-heterocyclic carbene (aNHC) based potassium complex was used as a transition metal-free catalyst for reduction of primary amides to corresponding primary amines under ambient conditions. Only 2 mol% loading of the catalyst exhibits a broad substrate scope including aromatic, aliphatic and heterocyclic primary amides with excellent functional group tolerance. This method was applicable for reduction of chiral amides and utilized for the synthesis of pharmaceutically valuable precursors on a gram scale. During mechanistic investigation, several intermediates were isolated and characterized through spectroscopic techniques and one of the catalytic intermediates was characterized through single-crystal XRD. A well-defined catalyst and isolable intermediate along with several stoichiometric experiments, in situ NMR experiments and the DFT study helped us to sketch the mechanistic pathway for this reduction process unravelling the dual role of the catalyst involving nucleophilic activation by aNHC along with Lewis acidic activation by K ions.