34438-71-6Relevant academic research and scientific papers
Persistent Room-Temperature Radicals from Anionic Naphthalimides: Spin Pairing and Supramolecular Chemistry
Huang, Wenhuan,Chen, Biao,Zhang, Guoqing
supporting information, p. 12497 - 12501 (2019/09/10)
N-Substituted naphthalimides (NNIs) have been shown to exhibit highly efficient and persistent room-temperature phosphorescence from an NNI-localized triplet excited state, when the N-substitution is a sufficiently strong donor and mediates an intramolecu
Application of a new kinetic method in the investigation of cleavage reactions of haloaromatic radical anions
Enemaerke, Rasmus J.,Christensen, Torben B.,Jensen, Henrik,Daasbjerg, Kim
, p. 1620 - 1630 (2007/10/03)
A simple kinetic method based on competition kinetics is presented for the measurement of cleavage rate constants of radical anions over the range of 107 - 5 × 109 s-1 in aprotic solvents. The standard potential for the formation of the radical anions may be extracted from the kinetic analysis as well. The method employs electrochemical steady-state or optical detection techniques and is an extension of the redox catalysis approach described previously in the literature. The applicability of the method is illustrated through a systematic study of the cleavage reactions for a number of short-lived haloaromatic radical anions. Interestingly, the radical anion of iodobenzene is found to be an intermediate in the homogeneous reduction of iodobenzene, even though recent investigations have shown that the corresponding heterogeneous reduction at an electrode surface proceeds by a concerted electron transfer-bond cleavage process. The nature of the cleavage reactions is discussed in terms of the activation driving force plot of the cleavage rate constants versus the relevant Gibbs energies. While the exergonic cleavage reactions follow a simple decay mechanism taking place at the halogen site, the endergonic processes are best described as intra-molecular electron transfers from the substituent to the carbon-halogen bond. Nevertheless, the overall intrinsic barrier is found to be relatively small (27-39 kJ mol-1) and it is suggested that the endergonic reactions may proceed by a stepwise mechanism, in which a σ* radical anion is formed as an intermediate prior to the formation of the dissociated products, the aryl radical and the halide. The above conclusions were supported by semi-empirical PM3 calculations of structures and charge distributions in the radical anions.
Ureas and amides as dipolar aprotic solvents in highly basic media. The dependence of kinetic basicity on solvent composition
Kankaanperae, Alpo,Scharlin, Pirketta,Kuusisto, Ilona,Kallio, Riitta,Bernoulli, Emma
, p. 169 - 174 (2007/10/03)
The basicity of dipolar aprotic solvent water HO systems with amides and ureas as the organic component has been studied kinetically because previous information is not available. excluding some H values measured for aqueous dimethylformamide (DMF) and tetramethylurea (TMU). It was found that the increase in basicity with the mole fraction of organic component is at least of the same magnitude as in aqueous dimethyl sulfoxide (DMSO). For instance, in the detritiation of chloroform-t the slopes of the plots log(k2/mol 1 dm3 s 1) vs. x(urea) varied between 11.4 14.6 (as compared to 11.0 in aqueous DMSO) when TMU and cyclic ureas. 1.3-dimethylimidazolidin-2-one (DMI) and 1.3-dimethyl-3.4.5.6-tetrahydropyrimidin-2(1H)-one (DMPU). were used as the organic component in solvent mixture. In aqueous TMU acidity functions H were extrapolated from kinetic results using linear free energy correlations. Agreement with literature values was evident. This method was also used to extrapolate the H values in aqueous DMPU. On the basis of present work aqueous ureas can be recommended as solvents in highly basic media. The utility of amides. dimethylformamide and dimethylacetamide. is limited by their instability in basic water solutions.
Solvent effects on the reduction mechanism of 9-chloroanthracene, 3-nitrobenzyl chloride and 3-chloroacetophenone
Jensen, Henrik,Daasbjerg, Kim
, p. 1151 - 1164 (2007/10/03)
The reduction mechanism of 9-chloroanthracene, 3-nitrobenzyl chloride and 3-chloroacetophenone has been investigated in detail by means of cyclic voltammetry and controlled potential bulk electrolysis. The investigation was carried out in a number of aprotic solvents in order to elucidate the importance of solvation phenomena on the various parameters associated with the reaction mechanism, i.e., clevage, hydrogen abstraction, protonation and dimerization rate constants as well as standard potentials. In this connection, the influence of the supporting electrolyte in terms of ion pairing and double layer effects has been considered. For the radical anions of 9-chloroanthracene and 3-nitrobenzyl chloride the logarithm of the cleavage rate constant shows a linear dependence on the Gutmann acceptor number and donor number, respectively, whereas no clear-cut correlation can be observed in the case of the radical anion of 3-chloroacetophenone. The rate constant obtained for the protonation reaction between 3-nitrobenzyl anion and 3-nitrobenzyl chloride is to an even higher extent influenced by the nature of the solvent. The trends in the solvent effects are discussed. Acta Chemica Scandinavica 1998.
Electrochemistry of electron-transfer probes. The role of the leaving group in the cleavage of radical anions of α-aryloxyacetophenones
Andersen, Mogens L.,Mathivanan,Wayner, Danial D. M.
, p. 4871 - 4879 (2007/10/03)
The formal reduction potential (E°) of α-phenoxyacetophenone has been determined from the voltammetric peak potential obtained by linear sweep voltammetry in combination with the rate constant for fragmentation of the radical anion which had been determin
Unimolecular rearrangements of carbanions in the gas phase. 2. Cyclopropyl anions
Chou, Phillip K.,Dahlke, Gregg D.,Kass, Steven R.
, p. 315 - 324 (2007/10/02)
We have examined the gas-phase unimolecular rearrangements of a series of substituted cyclopropyl anions (CHXCH2CY-; X - H, Y = Ph, CHO, and CM; X = Y = CO2CH3) with a variable temperature flowing afterglow device. The ring-opening barriers range from 19 to ≥36 kcal mol-1 and are well reproduced by ab initio molecular orbital calculations. An analysis of eight monosubstituted cyclopropyl anions reveals that the flexibility (ease of inversion) and thermodynamic stability of these ions account for their tendency to isomerize.
Rapid Cleavage Reactions of Haloaromatic Radical Anions Measured with Fast-Scan Cyclic Voltammetry
Wipf, David O.,Wightman, R. Mark
, p. 4286 - 4291 (2007/10/02)
Cyclic voltammetry at scan rates from 10 mV/s to 1E6 V/s has been used to characterize the reduction of aryl and benzyl halides in acetonitrile solutions containing 0.6 M tetraethylammonium perchlorate.The use of very rapid scan rates is made possible with electrodes of micrometer dimensions.The kinetics and mechanism of the reduction process have been evaluated by digital simulation of the recorded voltammograms.The radical anion generated at the electrode surface is found to have a half-life ranging from less than 100 ns in the case of 4'-bromoacetophenone to 70 ms for the case of m-nitrobenzyl chloride.The reduction mechanism for the aryl halides is consistent with the ECE-DISP1 mechanism.Thus following initial one-electron reduction, halogen bond cleavage occurs resulting in a radical that is subsequently reduced.For the compounds with relatively long half-lives (>1ms) the results in thus work are in good agreement with prior investigations with cyclic voltammetry.Good agreement is also obtained with compounds that have a short half-life ( ca. 1 μs) which have been characterized by the technique of redox catalysis.However, the measured rate constants differ with previously reported values which were estimated or measured at the extreme time limits of classical electrochemical techniques.
