KINETICS OF ALKENE OXIDATION BY CATIONIC TRANS-DIOXO-RUTHENIUM(VI) COMPLEXES - EFFECT OF DRIVING FORCE ON RATE CONSTANTS

被引:43
作者
CHE, CM
LI, CK
TANG, WT
YU, YY
机构
来源
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1992年 / 21期
关键词
D O I
10.1039/dt9920003153
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The kinetics of alkene oxidation by a series of isostructural trans-dioxoruthenium(VI) complexes with E-degrees(Ru(VI)-Ru(V)) ranging from 0.23 to 0.7 V vs. saturated calomel electrode has been investigated in acetonitrile. The experimental rate law is rate = k2[Ru(VI)][alkene]. A linear free-energy relationship between log k2 and E-degrees(Ru(VI)-Ru(V)) for the oxidation of styrene and norbornene has been observed. Both steric and electronic effects of alkenes as well as the E-degrees of the dioxoruthenium(VI) complexes affect the rate constants. For the oxidation of para-substituted styrenes, a linear Hammett plot of log k2 versus sigma+ for the para substituents with a rho value of -2.1 was found. A charge-transfer mechanism alone is insufficient to explain the experimental findings.
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页码:3153 / 3158
页数:6
相关论文
共 28 条
[1]   RUTHENIUM OXO COMPLEXES OF MACROCYCLIC TERTIARY-AMINES - SYNTHESIS, ELECTROCHEMISTRY, AND REACTIVITIES OF RUTHENIUM OXO COMPLEXES OF MESO-2,3,7,11,12-PENTAMETHYL-3,7,11,17-TETRA-AZABICYCLO[11.3.1]HEPTADECA-1(17),13,15-TRIENE (L1), AND X-RAY CRYSTAL-STRUCTURE OF TRANS-[RUIVL1(O)(NCO)]CLO4 [J].
CHE, CM ;
TANG, WT ;
LEE, WO ;
WONG, WT ;
LAI, TF .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1989, (10) :2011-2016
[2]   NOVEL RUTHENIUM OXO COMPLEXES OF SATURATED MACROCYCLES WITH NITROGEN AND OXYGEN DONORS AND X-RAY CRYSTAL-STRUCTURE OF TRANS-[RUIV(L)O(H2O)][CLO4]2 [J].
CHE, CM ;
TANG, WT ;
WONG, WT ;
LAI, TF .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (25) :9048-9056
[3]   SYNTHESIS, REACTIVITIES, AND STRUCTURAL STUDIES ON HIGH-VALENT RUTHENIUM OXO COMPLEXES - RUTHENIUM(IV), RUTHENIUM(V), AND RUTHENIUM(VI) OXO COMPLEXES OF TERTIARY AMINE LIGANDS [J].
CHE, CM ;
LAI, TF ;
WONG, KY .
INORGANIC CHEMISTRY, 1987, 26 (14) :2289-2299
[4]   A HIGH-VALENT RUTHENIUM(VI) DIOXO CATION OF 1,4,8,11-TETRAMETHYL-1,4,8,11-TETRAAZACYCLOTETRADECANE [J].
CHE, CM ;
WONG, KY ;
POON, CK .
INORGANIC CHEMISTRY, 1985, 24 (12) :1797-1800
[5]   SYNTHESIS, ELECTROCHEMISTRY, AND REACTIVITIES OF TRANS-[RU(VI)(L)O2]2+ (L = N,N'-DIMETHYL-N,N'-BIS(2-PYRIDYLMETHYL)PROPYLENEDIAMINE [J].
CHE, CM ;
TANG, WT ;
LI, CK .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1990, (12) :3735-3739
[6]   A HIGH-VALENT DIOXORUTHENIUM(VI) COMPLEX OF 2,2'-BIPYRIDINE (BPY) - PREPARATION AND CHARACTERIZATION OF TRANS-[RUVI(BPY)2O2]2+ [J].
CHE, CM ;
WONG, KY ;
LEUNG, WH ;
POON, CK .
INORGANIC CHEMISTRY, 1986, 25 (03) :345-348
[7]   SYNTHESIS, REACTIVITIES AND ELECTROCHEMISTRY OF TRANS-DIOXO-RUTHENIUM(VI) COMPLEXES OF PI-AROMATIC DIIMINES [J].
CHE, CM ;
LEUNG, WH ;
LI, CK ;
POON, CK .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1991, (03) :379-384
[8]  
CHE CM, IN PRESS ADV INORG
[9]   STUDIES ON TRANSITION-METAL OXO AND NITRIDO COMPLEXES .10. NEW OXO RUTHENIUM AND OXO OSMIUM PYRIDINE COMPLEXES, AND USE OF THE FORMER AS CATALYSTS FOR OXIDATION OF ALCOHOLS [J].
ELHENDAWY, AM ;
GRIFFITH, WP ;
TAHA, FI ;
MOUSSA, MN .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1989, (05) :901-906
[10]   STUDIES ON TRANSITION-METAL OXO AND NITRIDO COMPLEXES .9. PERIODATO AND TELLURATO OXO-RUTHENIUM COMPLEXES AS ORGANIC OXIDANTS - X-RAY CRYSTAL-STRUCTURE OF TRANS-NAK5[RUO2(HLO6)2].8H2O [J].
ELHENDAWY, AM ;
GRIFFITH, WP ;
PIGGOTT, B ;
WILLIAMS, DJ .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1988, (07) :1983-1988