Marcus Analysis of Ambident Reactivity

被引：47
|
作者：
Breugst, Martin [1 ]
Zipse, Hendrik [1 ]
Guthrie, J. Peter [2 ]
Mayr, Herbert [1 ]
机构：
[1] Univ Munich, Dept Chem, D-81377 Munich, Germany
[2] Univ Western Ontario, London, ON N6A 3K7, Canada
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2010年 / 49卷 / 30期
关键词：
ab initio calculations; computational chemistry; Marcus theory; nucleophilic substitution; transition states; ELECTRON-TRANSFER REACTIONS; MODEL S(N)2 REACTIONS; SOFT ACIDS; INTRINSIC BARRIERS; SN2; REACTIONS; LEAST MOTION; BASES HSAB; CH3X+F-X; HARD; PRINCIPLE;
D O I：
10.1002/anie.201001574
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
A better approach to ambident reactivity: The principle of hard and soft acids and bases (HSAB) cannot rationalize the reactivities of even the prototypical ambident nucleophiles shown in the picture. Marcus theory, which describes activation energies by a combination of intrinsic and thermodynamic terms, is a superior alternative. © 2010 Wiley-VCH Verlag GmbH & Co.KGaA.
引用
收藏
页码：5165 / 5169
页数：5
相关论文
共 50 条
  • [1] The Reactivity of Ambident Nucleophiles: Marcus Theory or Hard and Soft Acids and Bases Principle?
    Wang, Yi-Gui
    Barnes, Ericka C.
    Kaya, Savas
    Sharma, Vinit
    JOURNAL OF COMPUTATIONAL CHEMISTRY, 2019, 40 (31) : 2761 - 2777
  • [2] A novel ambident reactivity of azolylacroleins
    Nagy, Ildiko
    Hajos, Gyoergy
    Riedl, Zsuzsanna
    Egyed, Orsolya
    Papai, Imre
    TETRAHEDRON, 2007, 63 (22) : 4730 - 4736
  • [3] Ambident reactivity of the cyanate anion
    Schaller, Heike F.
    Schmidhammer, Uli
    Riedle, Eberhard
    Mayr, Herbert
    CHEMISTRY-A EUROPEAN JOURNAL, 2008, 14 (13) : 3866 - 3868
  • [4] Isolation and Ambident Reactivity of a Chlorogermylenoid
    Suzuki, Yuko
    Sasamori, Takahiro
    Guo, Jing-Dong
    Nagase, Shigeru
    Tokitoh, Norihiro
    CHEMISTRY-A EUROPEAN JOURNAL, 2016, 22 (39) : 13784 - 13788
  • [5] ANALYSIS OF AMBIDENT REACTIVITY OF ALKALINE-SALTS OF PHOSPHORUS MONOTHIOACIDS
    MASTRYUKOVA, TA
    PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS, 1987, 30 (1-2): : 209 - 212
  • [6] Competition between N and O: use of diazineN-oxides as a test case for the Marcus theory rationale for ambident reactivity
    Sheehy, Kevin J.
    Bateman, Lorraine M.
    Flosbach, Niko T.
    Breugst, Martin
    Byrne, Peter A.
    CHEMICAL SCIENCE, 2020, 11 (35) : 9630 - 9647
  • [7] Farewell to the HSAB Treatment of Ambident Reactivity
    Mayr, Herbert
    Breugst, Martin
    Ofial, Armin R.
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (29) : 6470 - 6505
  • [8] Ambident reactivity of the nitrite ion revisited
    Tishkov, AA
    Schmidhammer, U
    Roth, S
    Riedle, E
    Mayr, H
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (29) : 4623 - 4626
  • [9] Control of the ambident reactivity of the nitrite ion
    Dong, Hai
    Rahm, Martin
    Thota, Niranjan
    Deng, Lingquan
    Brinck, Tore
    Ramstrom, Olof
    ORGANIC & BIOMOLECULAR CHEMISTRY, 2013, 11 (04) : 648 - 653
  • [10] Ambident Reactivity of Bis(Diisopropylamino)carbene
    Poliakov, Dmytro
    Shevchenko, Igor
    EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2010, 2010 (13) : 2449 - 2451
12345