Selectivity from a kinetic point of view: nonlinear behavior of logarithmic product ratios as a function of the reciprocal temperature

被引：26

作者：

Heller, D

Buschmann, H

机构：

[1] Univ Rostock, Inst Organ Katalyseforsch, D-18055 Rostock, Germany

[2] Grunenthal GmbH, Forschungszentrum, D-52078 Aachen, Germany

来源：

TOPICS IN CATALYSIS | 1998年 / 5卷 / 1-4期

关键词：

nonlinear temperature behavior; Eyring plot; modified Eyring plot; selectivity; selection process; enantioselectivity; selection level; isoinversion principle; isoinversion temperature; inversion temperature; kinetics; catalysis; asymmetric hydrogenation; dihydroxylation; cocyclization;

D O I：

10.1023/A:1019185532627

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

The influence of the temperature on selectivity is described under special consideration of nonlinearities in the corresponding modified Eyring plots. Reasons for the experimentally well-known behavior are discussed. Furthermore, the conditions for nonlinear temperature behavior are quantified and a concept is described which allows the determination of the temperature dependence of a single reaction pathway in a selection process.

引用

页码：159 / 176

页数：18

共 87 条

[81] Density functional study of the [2+2]- and [2+3]-cycloaddition mechanisms for the osmium-catalyzed dihydroxylation of olefins
Torrent, M
Deng, LQ
Duran, M
Sola, M
Ziegler, T
[J]. ORGANOMETALLICS, 1997, 16 (01) : 13 - 19
[82] INFLUENCE OF THE REACTION TEMPERATURE ON THE ENANTIOSELECTION OF STYRENE HYDROFORMYLATION CATALYZED BY PTCL(SNCL3) COMPLEXES OF P-ARYL-SUBSTITUTED CHIRAL LIGANDS
TOTH, I
GUO, I
HANSON, BE
[J]. ORGANOMETALLICS, 1993, 12 (03) : 848 - 852
[83] COBALT-MEDIATED [2+2+2]-CYCLOADDITIONS - A MATURING SYNTHETIC STRATEGY
VOLLHARDT, KPC
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1984, 23 (08): : 539 - 556
[84] Solarphotocalalytic co-cyclisation of acetylene and nitriles in water
Wagler, P
Heller, B
Ortner, J
Funken, KH
Oehme, G
[J]. CHEMIE INGENIEUR TECHNIK, 1996, 68 (07) : 823 - 826
[85] WAKATSUKI Y, 1976, SYNTHESIS-STUTTGART, P26
[86] Wakatsuki Y., 1973, TETRAHEDRON LETT, V14, P3383
[87] CONJUGATE ADDITIONS OF ORGANOCUPRATES TO CYCLOALKENONE COMPLEXES OF THE CHIRAL RHENIUM LEWIS-ACID [(ETA(5)-C5H5)RE(NO)(PPH(3))](+) - ENANTIOSELECTIVE SYNTHESES OF 3-SUBSTITUTED CYCLOALKANONES
WANG, Y
GLADYSZ, JA
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1995, 60 (04) : 903 - 909

← 1 2 3 4 5 6 7 8 9 →