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1.
Dr. Jordan Donat Mr. Patrick Dubourdeaux Dr. Martin Clémancey Dr. Julia Rendon Clara Gervasoni Mr. Morgan Barbier Jessica Barilone Dr. Jacques Pécaut Prof. Dr. Serge Gambarelli Prof. Dr. Pascale Maldivi Prof. Dr. Jean-Marc Latour 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202201875
Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from FeII and FeIII precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an FeIV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the FeII precursor was expected by a two-electron oxidative addition, its formation from an FeIII precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the FeIII precursor, an FeIII tosyliodinane adduct was formed and decomposed into an FeV tosylimido species which generated the catalytically active FeIV tosylimide through a comproportionation process with the FeIII precursor. 相似文献
2.
Synthesis,Electronic Properties and WOLED Devices of Planar Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons
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Dr. François Riobé Rózsa Szűcs Dr. Pierre‐Antoine Bouit Dr. Denis Tondelier Bernard Geffroy Fátima Aparicio Julia Buendía Prof. Luis Sánchez Prof. Régis Réau Prof. László Nyulászi Prof. Muriel Hissler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(17):6547-6556
We describe the synthesis and the physical properties of polyaromatic hydrocarbons (PAHs) containing a phosphorus atom at the edge. In particular, the impact of the successive addition of aromatic rings on the electronic properties was investigated by experimental (UV/Vis absorption, fluorescence, cyclic voltammetry) and theoretical studies (DFT). The physical properties recorded in solution and in the solid state showed that the P‐containing PAHs exhibit properties expected for an emitter in white organic light‐emitting diodes (WOLEDs). 相似文献
3.
Julia K Pruns Jens-Peter Vietzke Manfred Strassner Claudius Rapp Ulrich Hintze Wilfried A K?nig 《Rapid communications in mass spectrometry : RCM》2002,16(3):208-211
A new solvent-free sample preparation method using silver trifluoroacetate (AgTFA) was developed for the analysis of low molecular weight paraffins and microcrystalline waxes by laser desorption/ionization time-of-flight mass spectrometry (LDI-TOFMS). Experiments show that spectral quality can be enhanced by dispersing AgTFA directly in liquid paraffins without the use of additional solvents. This preparation mixture is applied directly to the MALDI probe. Solid waxes could be examined by melting prior to analysis. The method also provides sufficiently reproducible spectra that peak area ratios between mono- and bicyclic alkane peaks indicated variations in the cycloalkane content of paraffin samples. Dehydrogenation of hydrocarbons observed during the desorption/ionization process was studied by analysis of alkane standards. 相似文献
4.
A method of solving the problem of sound radiation from a plate with elements of different thickness in its plane is proposed, and the results obtained with this method are presented. It is shown that the main sources of sound radiation are the inhomogeneous flexural fields formed in the elements on both sides of their joint. 相似文献
5.
Three types of transparency of a semiconductor superlattice, namely, self-induced, induced, and selective transparency, were studied. The conditions of their existence and the causes of their destruction were revealed. It was shown that the state of self-induced transparency, which is unstable in a harmonic field, can be stable in a biharmonic field. 相似文献
6.
R. A. Kotel’nikova G. N. Bogdanov G. V. Zotina V. S. Romanova Z. N. Parnes 《Physics of the Solid State》2002,44(3):576-577
Efficient quenching of eosin phosphorescence by amino-acid derivatives of fullerene (AADFs) such as C60-alanine and C60-glycine in aqueous solutions indicates the possibility of transferring electrons from eosin to fullerene upon collisions or in the exciplex state. To investigate electron transfer in the protein structure, we studied the process of incorporation of C60-alanine and C60-glycine into the heme pocket of myoglobin by controlling Förster quenching. The dissociation constant for the protein-AADF complex was estimated. 相似文献
7.
A. A. Lamberov E. V. Dement’eva Kh. Kh. Gil’manov S. R. Egorova N. V. Romanova 《Russian Journal of Applied Chemistry》2006,79(9):1453-1457
The effect of the paste molding pressure on the physicomechanical and texture characteristics of catalysts was studied. An indirect criterion is suggested to evaluate the molding pressure in industrial extruders, whose optimal value ensures good physicomechanical properties of the catalysts and kinetic control over the catalyzed reaction. The results obtained were verified in paste molding on various industrial extruders, and this enabled the optimal choice of the molding equipment. 相似文献
8.
L. T. Eremenko L. B. Romanova M. E. Ivanova I. L. Eremenko S. E. Nefedov Yu. T. Struchkov 《Russian Chemical Bulletin》1994,43(4):619-623
An effective method of esterification of 1,4-cubanedicarboxylic acid with alkylsulfuric acids is proposed. The derivatives of alkanols with substantially different pKa Valus are obtained in high yields. Molecular structures of the esters obtained are confirmed by various methods. The X-ray study showed a remarkable effect of the nature of an alkyl radical on the geometry of the cubane core.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp.668–672, April, 1994.The authors thank Dr. G. V. Lagodzinskaya for analyzing the NMR spectra and for useful discussions. 相似文献
9.
Damien P. Foster Carlo Vanderzande Julia Yeomans 《Journal of statistical physics》1992,69(3-4):857-868
We study the zero-temperature behavior of several simple models for randomly self-interacting polymers in one and 1+1 dimensions. Results are based on exact enumeration and closed-form expressions. 相似文献
10.
The theory for the calculation of the frequency-dependent hyperpolarizabilities β(?2ω; 0, ω), β(?ω; 0, ω), and β(0; ω, ?ω) is discussed. New relations between these tensors are derived for those wave functions that obey the time-dependent Hellmann–Feynman theorem (e.g., the self-consistent field [SCF] or the exact wave function). Using second-order Møller–Plesset perturbation theory (MP2), expressions are obtained for the hyperpolarizabilities in terms of derivatives of appropriately defined linear polarizability tensors with respect to a static electric field. Results are presented for ammonia and formaldehyde for the optical Kerr effect and for secondharmonic generation. These results indicate that it is desirable to determine the frequency-dependent contribution to the hyperopolarizability at the MP2 rather than the SCF level of theory, in cases where the static hyperpolarizability has a large contribution from electron correlation and/or where the frequency-dependent contribution may be more significant, such as for secondharmonic generation. 相似文献