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1.
L. A. Shundrin I. G. Irtegova A. D. Rogachev V. A. Reznikov 《Russian Chemical Bulletin》2005,54(5):1178-1184
The electrochemical reduction of 3,3′-bi(2-R-5,5-dimethyl-4-oxopyrrolinylidene) 1,1′-dioxides (R = CF3, Me, Ph, But), which are cyclic dinitrons with conjugated C=C bond, in acetonitrile is an EE process producing stable radical anions and
dianions, whereas the electrochemical oxidation is an EEC (R = Me, Ph) or EE process (R = But) with formation of radical cations (except for the case of R = CF3) and dications (R = But) stable under standard conditions. Radical cations of the dioxides with R = Me, Ph, and But and radical anions of the whole series of the compounds studied, including R = CF3, were characterized by ESR spectroscopy combined with electrochemical measurements and quantum-chemical calculations. The
electrochemical behavior of the But-substituted dinitron is unique: the EE processes in the region of negative and positive potentials with formation of the
dianion, radical anion, radical cation, and dication stable at T = 298 K were observed for the first time within one cycle of potential sweep in the CV curve measured in MeCN.
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1148–1154, May, 2005. 相似文献
2.
Synthesis and EPR/UV/Vis‐NIR Spectroelectrochemical Investigation of a Persistent Phosphanyl Radical Dication 下载免费PDF全文
Kai Schwedtmann Stephen Schulz Felix Hennersdorf Prof. Dr. Thomas Strassner Dr. Evgenia Dmitrieva Prof. Dr. Jan J. Weigand 《Angewandte Chemie (International ed. in English)》2015,54(38):11054-11058
The reaction of the bis(imidazoliumyl)‐substituted PI cation [(2‐ImDipp)P(4‐ImDipp)]+ ( 10 +) (2‐Im=imidazolium‐2‐yl; 4‐Im=imidazolium‐4‐yl; Dipp=2,6‐di‐isopropylphenyl) with trifluoromethanesulfonic acid (HOTf) or methyl trifluoromethylsulfonate (MeOTf) yields the corresponding protonated [(2‐ImDipp)PH(4‐ImDipp)]2+ ( 11 2+) and methylated [(2‐ImDipp)PMe(4‐ImDipp)]2+ ( 12 2+) dications, respectively. EPR/UV/Vis‐NIR spectroelectrochemical investigation of the low‐coordinated PI cation 10 + predicted a stable and “bottleable” P‐centered radical dication [(2‐ImDipp)P(4‐ImDipp)]2+. ( 13 2+.). The reaction of 10 + with the nitrosyl salt NO[OTf] yields the persistent phosphanyl radical dication 13 2+. as triflate salt in crystalline form. Quantum chemical investigation revealed an exceptional high spin density at the P atom. 相似文献
3.
I. F. Gun'kin 《Russian Chemical Bulletin》1993,42(11):1887-1890
Disproportionation reactions of various phenyl- and thienylthallium dicarboxylates with copper in acetonitrile have been carried out. The reaction mechanism proposed involves the participation of the ArTl2+ dication and various cationic pairs of the dication and the intermediate formation of organothallium radicals.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1970–1973, November, 1993. 相似文献
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N. E. Shevchenko V. G. Nenajdenko V. M. Muzalevskii E. S. Balenkova 《Russian Chemical Bulletin》2004,53(8):1726-1728
Stereochemistry of the addition of a cyclic disulfonium dication generated from 1,4-dithiane to alkenes was studied. The reaction is nonstereospecific, which can be attributed to a stepwise mechanism.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1660–1662, August, 2004. 相似文献
6.
The mechanism of the bond-forming reaction between C(7)H(6) (2+) and C(2)H(2) to yield C(9) entities has been investigated by density functional theory calculations with close comparison with experimental data. It is shown that the reaction produces the C(9)H(6) (2+) and C(9)H(7) (2+) di-cations with geometries most probably derived from the indene skeleton. In comparison, the formation of linear structures of di-cations is much more energy-demanding and therefore appears improbable. 相似文献
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Dr. Christopher J. Shaffer Dr. Detlef Schröder Dr. Christian Alcaraz Dr. Ján Žabka Dr. Emilie‐Laure Zins 《Chemphyschem》2012,13(11):2688-2698
Even in the highly diluted gas phase, rather than electron transfer the benzene dication C6H62+ undergoes association with dinitrogen to form a transient C6H6N22+ dication which is best described as a ring‐protonated phenyl diazonium ion. Isotopic labeling studies, photoionization experiments using synchrotron radiation, and quantum chemical computations fully support the formation of protonated diazonium, which is in turn a prototype species of superacidic chemistry in solution. Additionally, reactions of C6H62+ with background water involve the transient formation of diprotonated phenol and, among other things, afford a long‐lived C6H6OH22+ dication, which is attributed to the hydration product of Hogeveen’s elusive pyramidal structure of C6H62+, as the global minimum of doubly ionized benzene. Nitrogen is essential for the formation of the C6H6OH22+ dication in that it mediates the formation of the water adduct, while the bimolecular encounter of the C6H62+ dication with water only leads to (dissociative) electron transfer. 相似文献
9.
Andrii O. Gerasov Iffat H. Nayyar Artëm E. Masunov Olga V. Przhonska Olexiy D. Kachkovsky Dmytro O. Melnyk Olexiy B. Ryabitsky Olexander O. Viniychuk 《International journal of quantum chemistry》2012,112(14):2659-2667
The quantum‐chemical investigations by ab initio method (restricted Hartree–Fock/6‐31G**) have been performed for a series of unsubstituted, monosubstituted, and disubstituted neutral polyenes and their double charged cations. The waves of charge alternation (characterized by the difference in the electron densities at the nearest carbon atoms or Δq function) and bond length alternation (characterized by the lengths difference of the nearest carbon–carbon bonds or Δl function) are reported. Comparisons are made with the corresponding monocationic polymethine molecules. We found that ionization by two electrons results in formation of two solitonic waves of charge alternation, rather than superposition of two overlapping solitonic waves into one. These waves behave similar to two independent elastic particles, which do not penetrate into each other despite the special confinement by the length of chromophore π‐system. In monosubstituted polyene dication, Δq and Δl functions contain two waves each; however, only one wave is mobile and sensitive to a change of the chemical nature of the terminal group, whereas the second wave remains practically unchanged. The introduction of one oxymethyl or phenyl terminal groups leads to a relatively small shift of the mobile wave from the center to a direction of the terminal group. The effect of the amino or tropilium terminal groups is much more pronounced and leads to a shift of the mobile wave to the end of the molecule. In disubstituted polyene dication, both solitonic waves become mobile and shift symmetrically to both ends. The general principles of the charge localization described in this study may be used in molecular design and fine‐tuning of the charge transport properties in plastic photovoltaics and other organic semiconducting materials. © 2012 Wiley Periodicals, Inc. 相似文献
10.
Giuliano Bandoli Alessandro Dolmella Stefano Gatto 《Journal of chemical crystallography》1995,25(3):143-145
A X-ray crystal structure determination of the title compound was carried out. A comparison of the relevant bond distances and angles in the ring system with other published structures showed that protonation has an influence on the ring geometry. 相似文献