Conditions for maxima and minima as inversion points in the temperature dependence of selection processes

被引:10
作者
Heller, D
Buschmann, H
Neumann, H
机构
[1] Univ Rostock eV, Inst Organ Katalyseforsch, D-18055 Rostock, Germany
[2] Grunenthal GmbH, Forschungszentrum, D-52078 Aachen, Germany
来源
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 | 1999年 / 02期
关键词
D O I
10.1039/a808392d
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The analytical expression for deviations from linear behavior of Logarithmic product ratios as a function of the reciprocal temperature (modified Eyring-plots) depends on the reason for the displacement. Therefore no generally Valid formula exists that describes the experimentally observed inversion temperatures, In the case of the disturbance of the establishment of preequilibria, general conditions for the existence of inversion temperatures associated with maxima and minima are deduced. In addition it is shown that the inversion temperature is independent of the activation entropy values for the reaction of the starting materials to the intermediates (Delta S(11)double dagger and Delta S(12)double dagger), but is dependent on the corresponding activation enthalpy values. The examples discussed show that the limiting conditions intersecting points of the absolute rates are not suitable for a general description of the complex behavior of the nonlinear temperature dependency.
引用
收藏
页码:175 / 181
页数:7
相关论文
共 37 条
  • [1] ACTIVATION PARAMETERS AND MULTISTAGE REACTION SCHEMES
    BLANDAMER, MJ
    SCOTT, JWM
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1988, 92 (22) : 6264 - 6269
  • [2] KINETIC COUPLING IN AND BETWEEN CATALYTIC CYCLES
    BOUDART, M
    DJEGAMARIADASSOU, G
    [J]. CATALYSIS LETTERS, 1994, 29 (1-2) : 7 - 13
  • [3] CHIRAL INDUCTION IN PHOTOCHEMICAL-REACTIONS .10. THE PRINCIPLE OF ISOINVERSION - A MODEL OF STEREOSELECTION DEVELOPED FROM THE DIASTEREOSELECTIVITY OF THE PATERNO-BUCHI REACTION
    BUSCHMANN, H
    SCHARF, HD
    HOFFMANN, N
    PLATH, MW
    RUNSINK, J
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (14) : 5367 - 5373
  • [4] THE ISOINVERSION PRINCIPLE - A GENERAL-MODEL OF CHEMICAL SELECTIVITY
    BUSCHMANN, H
    SCHARF, HD
    HOFFMANN, N
    ESSER, P
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1991, 30 (05) : 477 - 515
  • [5] LIGAND ELECTRONIC EFFECTS IN ASYMMETRIC CATALYSIS - ENHANCED ENANTIOSELECTIVITY IN THE ASYMMETRIC HYDROCYANATION OF VINYLARENES
    CASALNUOVO, AL
    RAJANBABU, TV
    AYERS, TA
    WARREN, TH
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (22) : 9869 - 9882
  • [6] Theory does not support an osmaoxetane intermediate in the osmium-catalyzed dihydroxylation of olefins
    Dapprich, S
    Ujaque, G
    Maseras, F
    Lledos, A
    Musaev, DG
    Morokuma, K
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (46) : 11660 - 11661
  • [7] Experimental and theoretical kinetic isotope effects for asymmetric dihydroxylation. Evidence supporting a rate-limiting ''(3+2)'' cycloaddition
    DelMonte, AJ
    Haller, J
    Houk, KN
    Sharpless, KB
    Singleton, DA
    Strassner, T
    Thomas, AA
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (41) : 9907 - 9908
  • [8] Catalytic asymmetric hydrosilylation with (triazolinylidene)rhodium complexes containing an axis of chirality
    Enders, D
    Gielen, H
    Breuer, K
    [J]. TETRAHEDRON-ASYMMETRY, 1997, 8 (21) : 3571 - 3574
  • [9] On the viability of oxametallacyclic intermediates in the (salen)Mn-catalyzed asymmetric epoxidation
    Finney, NS
    Pospisil, PJ
    Chang, S
    Palucki, M
    Konsler, RG
    Hansen, KB
    Jacobsen, EN
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1997, 36 (16): : 1720 - 1723
  • [10] Girard C, 1998, ANGEW CHEM INT EDIT, V37, P2923, DOI 10.1002/(SICI)1521-3773(19981116)37:21<2922::AID-ANIE2922>3.0.CO