Redox and acidity properties of alkyl- and arylamine radical cations and the corresponding aminyl radicals

被引:84
作者
Jonsson, M
Wayner, DDM
Lusztyk, J
机构
[1] Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa
[2] ABB Corporate Research
关键词
D O I
10.1021/jp961286q
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
In this work the pK(a)s of six alkyl- and arylamine radical cations in aqueous solution have been determined by means of laser flash photolysis. The corresponding N-nitrosamines were used as precursors for the aminyl radicals which, upon protonation, formed the amine radical cations. The following pK(a)s were obtained: 3.6 +/- 0.2, 7.6 +/- 0.3, 6.8 +/- 0.5, 5.3 +/- 0.5, 5.5 +/- 0.5, and 5.8 +/- 0.5 for the radical cations of diphenylamine, N-methylaniline, dimethylamine, diethylamine, pyrrolidine, and piperidine, respectively. In addition, the peak oxidation potentials of diphenylamine, N-methylaniline, aniline, diethylamine, pyrrolidine, and piperidine have been measured in aqueous solution and in acetonitrile using cyclic voltammetry. Furthermore, the one-electron reduction potentials of the diphenylaminyl radical and the N-methylanilinyl radical in acetonitrile were measured using photomodulation voltammetry. The results of this study and of previously published studies are discussed in terms of relative substituent and solvent effects.
引用
收藏
页码:17539 / 17543
页数:5
相关论文
共 41 条
[1]   HYDROGEN-BONDING .9. SOLUTE PROTON DONOR AND PROTON ACCEPTOR SCALES FOR USE IN DRUG DESIGN [J].
ABRAHAM, MH ;
DUCE, PP ;
PRIOR, DV ;
BARRATT, DG ;
MORRIS, JJ ;
TAYLOR, PJ .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1989, (10) :1355-1375
[2]   AMINOALKYL AND ALKYLAMINIUM FREE-RADICALS AND RELATED SPECIES - STRUCTURES, THERMODYNAMIC PROPERTIES, REDUCTION POTENTIALS, AND AQUEOUS FREE-ENERGIES [J].
ARMSTRONG, DA ;
RAUK, A ;
YU, DK .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (02) :666-673
[3]  
BARD AJ, 1984, ENCY ELECTROCHEMISTR, V15
[4]   VOLTAMMETRIC EVALUATION OF THE EFFECTIVE ACIDITIES (PKA') FOR BRONSTED ACIDS IN APROTIC-SOLVENTS [J].
BARRETTE, WC ;
JOHNSON, HW ;
SAWYER, DT .
ANALYTICAL CHEMISTRY, 1984, 56 (11) :1890-1898
[5]   PULSE-RADIOLYSIS STUDIES OF AMINOBENZENESULFONATES - FORMATION OF CATION RADICALS [J].
BEHAR, D ;
BEHAR, B .
JOURNAL OF PHYSICAL CHEMISTRY, 1991, 95 (19) :7552-7556
[6]   EQUILIBRIUM ACIDITIES IN DIMETHYL-SULFOXIDE SOLUTION [J].
BORDWELL, FG .
ACCOUNTS OF CHEMICAL RESEARCH, 1988, 21 (12) :456-463
[7]   BOND-DISSOCIATION ENERGIES OF THE N-H BONDS IN ANILINES AND IN THE CORRESPONDING RADICAL-ANIONS - EQUILIBRIUM ACIDITIES OF ANILINE RADICAL CATIONS [J].
BORDWELL, FG ;
ZHANG, XM ;
CHENG, JP .
JOURNAL OF ORGANIC CHEMISTRY, 1993, 58 (23) :6410-6416
[8]   NON-AROMATIC AMINIUM RADICALS [J].
CHOW, YL ;
DANEN, WC ;
NELSEN, SF ;
ROSENBLATT, DH .
CHEMICAL REVIEWS, 1978, 78 (03) :243-274
[9]   CYTOCHROME-P-450 CATALYSIS - RADICAL INTERMEDIATES AND DEHYDROGENATION REACTIONS [J].
DEMONTELLANO, PRO .
TRENDS IN PHARMACOLOGICAL SCIENCES, 1989, 10 (09) :354-359
[10]   MECHANISMS OF ACTION AND REACTIVITIES OF THE FREE-RADICALS OF INHIBITORS [J].
DENISOV, ET ;
KHUDYAKOV, IV .
CHEMICAL REVIEWS, 1987, 87 (06) :1313-1357