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排序方式: 共有941条查询结果,搜索用时 15 毫秒
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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
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Marius Lupu Adnana Zaulet Prof. Dr. Francesc Teixidor Prof. Dr. Eliseo Ruiz Prof. Dr. Clara Viñas 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(18):6888-6897
The metallacarborane [3,3′‐Co(1,2‐closo‐C2B9H11)2]? has been synthesized. This species allows the formation of redox couples in which both partners are negatively charged. The E1/2 potential can be tuned by adjusting the nature and number of substituents on B and C. The octaiodinated species [3,3′‐Co(1,2‐closo‐C2B9H7I4)2]? is the most favorable, as it is isolatable and stable in air. A DFT study on stability and redox potentials of complexes has been performed. 相似文献
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Marcelino Maneiro Manuel R. Bermejo M. Isabel Fernndez Ana M. Gonzlez‐Noya Alexei M. Tyryshkin Robin G. Pritchard 《无机化学与普通化学杂志》2003,629(2):285-290
A new MnIII‐Schiff base complex, [MnL(OH2)](ClO4) ( 1 ) (H2L = N, N′‐bis‐(3‐Br‐5‐Cl‐salicylidene)‐1, 2‐diimino‐2‐methylethane), an inorganic model of the catalytic center (OEC, Oxygen Evolving Complex) in photosystem II (PSII), has been synthesized and characterized by elemental analysis, IR and EPR spectroscopy, mass spectrometry, magnetic susceptibility measurement and the study of its redox properties by cyclic and normal pulse voltammetry. This complex mimics reactivity (showing a relevant photolytic activity), and also some structural characteristics (parallel‐mode MnIII EPR signal from partially assembled OEC cluster) of the natural OEC. The complex 1 was found to rearrange in solution into a crystallographically solved square‐pyramidal complex, [MnLL′] ( 2 ) (HL′ = 6‐bromo‐4‐chloro‐2‐cyanophenol), through a process, which probably liberates radical species (detected by EPR), and provokes a C—N bond cleavage in the ligand. A photo‐radical mechanism is discussed to explain this rearrangement. 相似文献
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Shock waves and the relevant Rankine-Hugoniot conditions may be inadequate even in simple cases. As an example, the electromagnetic field generated by a point charge, whose velocity jumps from0 to a constant value, not only jumps across a spherical surface expanding at light speed, but also includes a-distribution term. This suggests that the concept of higher order shock waves be introduced, the associated compatibility conditions being also deduced.
Sommario Il concetto di onda d'urto può rivelarsi inadeguato per descrivere situazioni anche semplici. A titolo di esempio, si determina esplicitamente l'espressione del campo elettromagnetico generato da una carica puntiforme la cui velocità passa istantaneamente da0 a un valore costante. Il campo elettromagnetico non solo è discontinuo attraverso una superficie sferica che si espande alla velocità della luce, ma include anche un termine che coinvolge la distribuzione. Ciò suggerisce di definire le onde d'urto di ordine superiore, per le quali si determinano le corrispondenti condizioni di compatibilità.相似文献
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