Equilibrium Acidities of Superacids

被引:238
作者
Kuett, Agnes [1 ]
Rodima, Toomas
Saame, Jaan
Raamat, Elin
Maeemets, Vahur
Kaljurand, Ivari
Koppel, Ilmar A.
Garlyauskayte, Romute Yu
Yagupolskii, Yurii L.
Yagupolskii, Lev M.
Bernhardt, Eduard
Willner, Helge
Leito, Ivo
机构
[1] Univ Tartu, Inst Chem, EE-50411 Tartu, Estonia
关键词
ACID-BASE EQUILIBRIA; WEAKLY COORDINATING ANIONS; GAS-PHASE; NONPOLAR MEDIA; BASICITY SCALE; CYANOCARBON CHEMISTRY; BRONSTED SUPERACIDS; EXTENSION; DESIGN; DFT;
D O I
10.1021/jo101409p
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
In this paper, we report the most comprehensive equilibrium superacidity scale that is available to date. Contrary to most of the past works, this scale is set up in a medium of constant composition and the obtained acidity values characterize the acidities of molecules rather than acidities of media. The current scale is thus complementary to the well-known H-0 scale in the information that it provides. The solvent used is 1,2-dichloroethane (DCE). DCE has very weak basic properties (but sufficiently high polarity) and is an appropriate solvent for measuring acidities of very strong acids of diverse chemical nature. DCE acidities of well-known superacids (CF3SO2OH, (CF3SO2)(2)NH, cyanocarbon acids, etc.) as well as common mineral acids (H2SO4, HI, HBr, etc.) are reported. Acidities of altogether 62 acids have been determined from 176 interlinked relative acidity measurements. The scale spans 15 orders of magnitude (from picric acid to 1,1,2,3,3-pentacyanopropene) and is expected to be a useful tool in design, use, and further acidity measurements of superacidic molecules.
引用
收藏
页码:391 / 395
页数:5
相关论文
共 41 条
[1]   EQUILIBRIUM ACIDITIES IN DIMETHYL-SULFOXIDE SOLUTION [J].
BORDWELL, FG .
ACCOUNTS OF CHEMICAL RESEARCH, 1988, 21 (12) :456-463
[2]   ACID-BASE STRENGTHS IN 1,2-DICHLOROETHANE [J].
BOS, M ;
DAHMEN, EAM .
ANALYTICA CHIMICA ACTA, 1973, 63 (01) :185-196
[4]   PROTON RESONANCE SHIFTS OF ACIDS IN LIQUID SULFUR DIOXIDE [J].
BROWNSTEIN, S ;
STILLMAN, AE .
JOURNAL OF PHYSICAL CHEMISTRY, 1959, 63 (12) :2061-2062
[5]   Chemistry - Superacids - It's a lot about anions [J].
DesMarteau, DD .
SCIENCE, 2000, 289 (5476) :72-73
[6]   DETERMINATION OF DISSOCIATION-CONSTANTS OF HJ, FSO3H AND CF3SO3H IN GLACIAL ACETIC-ACID [J].
ENGELBRECHT, A ;
RODE, BM .
MONATSHEFTE FUR CHEMIE, 1972, 103 (05) :1315-+
[7]   SYNTHESIS, PROPERTIES, AND REACTIONS OF BIS((TRIFLUOROMETHYL)SULFONYL) IMIDE, (CF3SO2)2NH [J].
FOROPOULOS, J ;
DESMARTEAU, DD .
INORGANIC CHEMISTRY, 1984, 23 (23) :3720-3723
[8]   Synthesis of new organic super acids -: N-(trifluoromethylsulfonyl)-imino derivatives of trifluoromethanesulfonic acid and bis(trifluoromethylsulfonyl)imide [J].
Garlyauskayte, RY ;
Chernega, AN ;
Michot, C ;
Armand, M ;
Yagupolskii, YL ;
Yagupolskii, LM .
ORGANIC & BIOMOLECULAR CHEMISTRY, 2005, 3 (12) :2239-2243
[9]   Synthesis and applications of superacids. 1,1,2,2-tetrafluoroethanesulfonic acid, supported on silica [J].
Harmer, Mark A. ;
Junk, Christopher ;
Rostovtsev, Vsevolod ;
Carcani, Liane G. ;
Vickery, Jemma ;
Schnepp, Zoe .
GREEN CHEMISTRY, 2007, 9 (01) :30-37
[10]   Design of Bronsted acid-assisted chiral Bronsted acid catalyst bearing a bis(triflyl) methyl group for a Mannich-type reaction [J].
Hasegawa, Aiko ;
Naganawa, Yuki ;
Fushimi, Makoto ;
Ishihara, Kazuaki ;
Yamamoto, Hisashi .
ORGANIC LETTERS, 2006, 8 (15) :3175-3178