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101.
Braunstein P Siri O Taquet JP Yang QZ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(15):3817-3821
Their pH-controlled reactivity places the N,N'-dialkyl-2-amino-5-lithium alcoholate-1,4-benzoquinonemonoimines [C(6)H(2)(NHCH(2)R') (=NCH(2)R')(=O)(OLi)] 7 (R'=tBu) and 8 (R'=p-C(6)H(4)-tBu) at the crossroads of a new versatile strategy for the preparation of two very different classes of substituted quinones. We describe new 2-(N-alkyl)amino-5-hydroxy-1,4-benzoquinones, which are parent molecules to biologically active substituted aminobenzoquinones, for which changes of the N-substituent will become readily possible. The results of the first X-ray structural determination of such compounds ([C(6)H(2)(NHCH(2)tBu)(OH)(=O)(2)] 13) are also reported and we compare the influence of the number of N-substituents of the C(6) ring on the supramolecular networks resulting from self-assembling of 13, zwitterionic N,N'-dineopentyl-2-amino-5-alcoholate-1,4-benzoquinonemonoiminium [C(6)H(2)(=NHCH(2)tBu)(2)(=O)(2)] 9 and N,N',N",N"'-tetraneopentyl-2,5-diamino-1,4-benzoquinone diimine [C(6)H(2)(NHCH(2)tBu)(2)(=NCH(2)tBu)(2)] 15. 相似文献
102.
Gerardo F. Santori Mónica L. Casella Guillermo J. Siri Hugo R. Adúriz Osmar A. Ferrettia 《Reaction Kinetics and Catalysis Letters》2002,75(2):225-230
The present work reports the effect of metal particle size on the selectivity to crotyl alcohol (SUOL) in the liquid phase hydrogenation of crotonaldehyde over SiO2 and a-Al2O3-supported Pt and Pt-Sn catalysts. It was demonstrated that, for the monometallic catalysts, a higher particle size led to a higher SUOL, while for the bimetallic catalysts, this effect was not so important. 相似文献
103.
104.
Didier Gigmes Anouk Gaudel‐Siri SylvainR.A. Marque Denis Bertin Paul Tordo Paola Astolfi Lucedio Greci Corrado Rizzoli 《Helvetica chimica acta》2006,89(10):2312-2326
A series of stable 2,2‐disubstituted 3‐(phenylimino)indol‐1‐oxyls, the alkoxyamines 3 , were prepared, characterized, and tested as possible candidates in controlled radical polymerization (CRP). The sturctures of 3d and 10 were additionally solved by X‐ray diffraction. The lability of the N? O(C) and (N)O? C bonds of compounds 3 were compared, and the possibility of N? O vs. O? C bond cleavage was evaluated by thermal degradation, ESR spin trapping, MS experiments, and DFT calculations. Alkoxyamines with a primary‐ or secondary‐alkyl group bound to the O‐atom of the nitroxide function (hexyl and i‐Pr) mainly underwent (undesired) N? O bond homolysis. When the O‐alkyl radical was a tertiary or a benzyl group (crotonyl or styryl), O? C bond cleavage occurred as the main process, thus suggesting a possible use of these compounds in CRP processes. 相似文献
105.
Hamad K Iwamoto A Miyazaki S Yamanaka N Guruge KS 《Journal of chromatographic science》2002,40(9):515-518
A high-performance liquid chromatographic procedure with a postcolumn fluorescence derivatization is developed for the analysis of oleandrin in bovine blood. Oleandrin is separated by an octadecylsilane-bonded column with a mobile phase containing dehydroascorbic acid. The effluent of the column is mixed with concentrated hydrochloric acid and passed through poly(tetrafluoroethylene) tubing maintained at 70 degrees C. The resultant fluorophores are detected at 465 nm with excitation at 348 nm. Simple solid-phase extraction using Sep-Pak tC2 is effective for sample purification. We found the minimal detectable quantity of oleandrin in plasma to be 1.5 ng/mL at a signal-to-noise ratio of 3:1. 相似文献
106.
Siri O Taquet JP Collin JP Rohmer MM Bénard M Braunstein P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(24):7247-7253
When a 2,5-diamino-1,4-benzoquinonediimine C6H2(=NR)2(NHR)2 (2) is used as a bridging ligand, new dinickel(II) complexes [(acac)Ni[mu-C6H2(=NPh)4]Ni(acac)] (3a: R=Ph) and [(acac)Ni[mu-C6H2(=NCH2tBu)4]Ni(acac)] (3b: R=CH2tBu) are obtained; upon one-electron oxidation of these complexes delocalized mixed-valence compounds are formed. An X-ray diffraction study on 3b reveals equalization of the bond lengths within each of the ligand 6 systems and a lack of conjugation between them. The oxidized state in 3b+ involves both the bridging quinonoid ligand and the metal centers, with a major contribution coming from the bridging ligand. Electrochemical and spectroscopic methods were used to study the influence of the N-substituents of the tetranitrogen donor ligands 2. In this combined experimental and theoretical (DFT) study, it is also shown that the electronic structure within the dinickel system can be altered by addition of a coordinating ligand such as pyridine. The latter favors the high-spin configuration with semi-occupied metal-centered orbitals, leading to a metal-metal interaction in the mixed-valence Ni(II)-Ni(III) 3b+ system. 相似文献
107.
108.
Vijai M. Santhini Christian Wckerlin Ale Cahlík Martin Ondr
ek Simon Pascal Adam Matj Oleksandr Stetsovych Pingo Mutombo Petr Lazar Olivier Siri Pavel Jelínek 《Angewandte Chemie (International ed. in English)》2021,60(1):439-445
Recently π–d conjugated coordination polymers have received a lot of attention owing to their unique material properties, although synthesis of long and defect‐free polymers remains challenging. Herein we introduce a novel on‐surface synthesis of coordination polymers with quinoidal ligands under ultra‐high vacuum conditions, which enables formation of flexible coordination polymers with lengths up to hundreds of nanometers. Moreover, this procedure allows the incorporation of different transition‐metal atoms with four‐ or two‐fold coordination. Remarkably, the two‐fold coordination mode revealed the formation of wires constituted by (electronically) independent 12‐membered antiaromatic macrocycles linked together through two C?C single bonds. 相似文献
109.
We present a combined theoretical approach based on analyzing molecular dynamics trajectories (at the nanosecond scale) generated by use of classical polarizable force fields and on quantum calculations to compute averaged hyperfine coupling constants. That method is used to estimate the constant of a prototypical nitroxide: the dimethylnitroxide. The molecule is embedded during the simulations in a cubic box containing about 500 water molecules and the molecular dynamics is generated using periodic conditions. Once the trajectories are achieved, the nitroxide and its first hydration shell molecules are extracted, and the coupling constants are computed by considering the latter aggregates by means of quantum computations. However, all the water molecules of the bulk are also accounted for during those computations by means of the electrostatic potential fitted method. Our results exhibit that in order to predict accurate and reliable coupling constants, one needs to describe carefully the out-of-plane motion of the nitroxide nitrogen and to sample trajectories with a time interval of 400 fs at least to generate an uncorrelated large set of nitroxide structures. Compared to Car-Parrinello molecular dynamics techniques, our approach can be used readily to compute hyperfine coupling constants of large systems, such as nitroxides of great size interacting with macromolecules such as proteins or polymers. 相似文献
110.
Alkylperoxyl spin adducts of pyrroline‐N‐oxide spin traps: Experimental and theoretical CASSCF study of the unimolecular decomposition in organic solvent,potential applications in water 下载免费PDF全文
Sergiu Lescic Hakim Karoui Micaël Hardy Laurence Charles Paul Tordo Olivier Ouari Anouk Gaudel‐Siri Didier Siri 《Journal of Physical Organic Chemistry》2017,30(10)
Spin trapping coupled with electron paramagnetic resonance spectroscopy is the most direct method for detection of very low concentrations of free radicals, and it has been intensively used to detect superoxide or alkylperoxyl radicals in biological systems, using cyclic nitrones as spin traps. The half‐life time of the ensuing spin adducts depends dramatically on the spin trap structure; however, their mechanism of decay has never been definitely established. We investigated at the MRMP2/CASSCF (MultiReference second‐order Møller‐Plesset perturbation theory/Complete Active Set Self Consistent Field) level of theory the mechanism of decay of methylperoxyl and tert‐butylperoxyl spin adducts formed with various cyclic nitrones. We showed that no transition state can be located for the O─O homolytic cleavage, which yields an intermediate biradical with the following sequence ?O─N─C─O?. Then, homolytic cleavage of the N─C bond yields a nitrosoaldehyde, through an early transition state with a very low activation energy. For each nitrone used as spin trap, electrospray ionization mass spectrometry analysis of the spin trapping mixture allowed to detect the presence of the expected nitrosoaldehyde. We generated tert‐butylperoxyl spin adducts in toluene, and we found a good correlation between their half‐life time and the bond dissociation energy of their peroxidic O─O bond. The theoretical method was then extended to hydroperoxyl spin adducts in water and provided promising results. 相似文献