13367-81-2Relevant articles and documents
Outer-Sphere Electron-Transfer Oxidation of 10,10'-Dimethyl-9,9',10,10'-tetrahydro-9,9-biacridine
Fukuzumi, Shunichi,Tokuda, Yoshihiro
, p. 8409 - 8413 (1992)
10,10'-Dimethyl-9,9',10,10'-tetrahydro-9,9'-biacridine acts as a unique two-electron donor in the electron-transfer oxidation with various organic oxidants.The rate-determining step is electron transfer from (AcrH)2 to oxidants, followed by facile cleavage of the C(9)-C bond of (AcrH)2.+ to yield the acridinyl radical (AcrH.) and 10-methylacridinium ion (AcrH+).The second electron transfer from AcrH. to oxidants is much faster than the initial electron transfer from (AcrH)2 to oxidants.On the other hand, the corresponding monomer, 10-methyl-9,10-dihydroacridine (AcrH2), acts as a normal hydride (two electrons and proton) donor in the reactions with oxidants.Rates of electron-transfer reactions from (AcrH)2 to various inorganic and organic one-electron oxidants depend solely on the one-electron-reduction potentials of the oxidants irrespective of the size of the oxidants, indicating that (AcrH)2 acts as a novel two-electron outer-sphere electron-transfer reagent.The one-electron-oxidation potential of (AcrH)2 (vs SCE) has been evaluated as 0.62 V, which is less positive than that of the corresponding monomer (0.80 V).
10-methylacridine dimer acting as a unique two-electron donor in the one-electron reduction of triphenylmethyl cation
Fukuzumi, Shunichi,Kitano, Toshiaki,Ishikawa, Masashi
, p. 5631 - 5632 (1990)
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Photoinduced Cleavage of the C-C Bond of 9-(1-Naphthylmethyl)-10-methyl-9,10-dihydroacridine by Perchloric Acid via Intramolecular Electron-Transfer Excitation
Fukuzumi, Shunichi,Tokuda, Yoshihiro,Fujita, Morifumi
, p. 8413 - 8416 (1992)
The C(9)-C bond of 9-(1-naphthylmethyl)-10-methyl-9,10-dihydroacridine (AcrHR) is readily cleaved by HClO4 in acetonitrile (MeCN) under irradiation of the absorption band of AcrHR to yield RH and AcrH+.The dependence of the fluorescence maximum on solvent dielectric constant indicates a highly polar singlet excited state with the dipole moment of ca. 15.6 D, while the fluorescence maximum of 9,10-dihydro-10-methylacridine (AcrH2) is insensitive to the solvent.The fluorescence of AcrHR is efficiently quenched by HClO4 with the rate constant of 8.6 * 109 M-1 s-1 in MeCN at 298 K.The same quenching rate constant has been obtained from the dependence of the quantum yields on for the photoinduced cleavage of the C-C bond of AcrHR by HClO4 in MeCN at 298 K.Thus, the photoinduced intramolecular charge transfer from the acridine moiety to the naphthalene moiety in AcrHR results in the generation of the highly polarized C-C bond which is susceptible to the cleavage by HClO4.The C(9)-C bond of AcrHR is also cleaved upon the intermolecular electron-transferoxidation of AcrHR by Fe(ClO4)3 and Fe(phen)3 and Fe(phen)33+ (phen = 1,10-phenanthroline) in MeCN to yield AcrH+, while the C(9)-H bond is cleaved in the case of AcrH2.
A classical but new kinetic equation for hydride transfer reactions
Zhu, Xiao-Qing,Deng, Fei-Huang,Yang, Jin-Dong,Li, Xiu-Tao,Chen, Qiang,Lei, Nan-Ping,Meng, Fan-Kun,Zhao, Xiao-Peng,Han, Su-Hui,Hao, Er-Jun,Mu, Yuan-Yuan
, p. 6071 - 6089 (2013/09/12)
A classical but new kinetic equation to estimate activation energies of various hydride transfer reactions was developed according to transition state theory using the Morse-type free energy curves of hydride donors to release a hydride anion and hydride acceptors to capture a hydride anion and by which the activation energies of 187 typical hydride self-exchange reactions and more than thirty thousand hydride cross transfer reactions in acetonitrile were safely estimated in this work. Since the development of the kinetic equation is only on the basis of the related chemical bond changes of the hydride transfer reactants, the kinetic equation should be also suitable for proton transfer reactions, hydrogen atom transfer reactions and all the other chemical reactions involved with breaking and formation of chemical bonds. One of the most important contributions of this work is to have achieved the perfect unity of the kinetic equation and thermodynamic equation for hydride transfer reactions. The Royal Society of Chemistry.
Comparison between electron transfer and nucleophilic reactivities of ketene silyl acetals with cationic electrophiles
Fukuzumi,Ohkubo,Otera
, p. 1450 - 1454 (2007/10/03)
The products and kinetics for the reactions of ketone silyl acetals with a series of p-methoxy-substituted trityl cations have been examined, and they are compared with those of outer-sphere electron transfer reactions from 10,10′-dimethyl-9,9′, 10, 10′- tetrahydro-9,9′-biacridine [(AcrH)2] to the same series of trityl cations as well as other electron acceptors. The C-C bond formation in the reaction of β,β-dimethyl-substituted ketene silyl acetal (1: (Me2C=C(OMe)OSiMe3) with trityl cation salt (Ph3C+ClO4-) takes place between 1 and the carbon of para-positon of phenyl group of Ph3C+, whereas a much less sterically hindered ketene silyl acetal (3: H2C=C(OEt)OSiEt3) reacts with Ph3C+ at the central carbon of Ph3C+. The kinetic comparison indicates that the nucleophilic reactivities of ketene silyl acetals are well correlated with the electron transfer reactivities provided that the steric demand at the reaction center for the C-C bond formation remains constant.
