Benzylic cations with triplet ground states: Computational studies of aryl carbenium ions, silylenium ions, nitrenium ions, and oxenium ions substituted with meta π donors

被引：0
|
作者：
Winter, Arthur H. [1 ]
Falvey, Daniel E. [1 ]
Cramer, Christopher J. [2 ]
Gherman, Benjamin F. [3 ]
机构：
[1] Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742-2021, United States
[2] Department of Chemistry, Supercomputer Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, MN 55455-0431, United States
[3] Department of Chemistry, California State University, Sacramento, 6000 J Street, Sacramento, CA 95819-6057, United States
来源：
Journal of the American Chemical Society | 2007年 / 129卷 / 33期
关键词：
Density functional theory (B3LYP/6-31G(d,p)) was used to predict the effect of meta substitution on aryl cationic (Ar-X+) species, including aryloxenium ions, arylsilylenium ions, arylnitrenium ions, and arylcarbenium ions. Multireference second-order perturbation theory (CASPT2) calculations were used to benchmark the quantitative accuracy of the DFT calculations for representative systems. Substituting the meta positions on these species with π donors stabilizes a π,π* diradical state analogous to the wellknown m-xylylene diradical. Notably, the 3,5-bis(N,N-dimethylamino)benzyl cation is predicted to have a triplet ground state by 1.9 kcal/mol by DFT and to have essentially degenerate singlet-triplet states at the CASPT2(10,9) level of theory. Adding electron-withdrawing CF3 groups to the exocyclic carbon of this meta-disubstituted benzyl cation further increases the predicted singlet-triplet gap in favor of the triplet. Other aryl cationic species substituted with strong π electron-donating groups in the meta positions are predicted to have low-energy or ground-state triplet stales. Systems analogous to the naphthaquinodimethane diradicals are also reported. © 2007 American Chemical Society;
D O I：
暂无
中图分类号：
学科分类号：
摘要：
Journal article (JA)
引用
收藏
页码：10113 / 10119
相关论文
共 34 条
  • [1] Benzylic cations with triplet ground states:: Computational studies of aryl carbenium ions, silylenium ions, nitrenium ions, and oxenium ions substituted with meta π donors
    Winter, Arthur H.
    Falvey, Daniel E.
    Cramer, Christopher J.
    Gherman, Benjamin F.
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (33) : 10113 - 10119
  • [2] THEORETICAL-STUDIES OF POLYVINYL-SUBSTITUTED CARBENIUM AND SILYLENIUM IONS
    TRUONG, T
    GORDON, MS
    BOUDJOUK, P
    ORGANOMETALLICS, 1984, 3 (03) : 484 - 487
  • [3] EXPERIMENTAL AND THEORETICAL-STUDIES OF IMIDAZOLE NITRENIUM IONS AND CARBENIUM IONS
    BOLTON, JL
    MCCLELLAND, RA
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 1988, 195 : 431 - ORGN
  • [4] Aryl Nitrenium and Oxenium Ions with Unusual High-Spin π,π* Ground States: Exploiting (Anti)Aromaticity
    Qiu, Yunfan
    Fischer, Logan J.
    Dutton, Andrew S.
    Winter, Arthur H.
    JOURNAL OF ORGANIC CHEMISTRY, 2017, 82 (24): : 13550 - 13556
  • [5] Discrete Existence of Singlet Nitrenium Ions Revisited: Computational Studies of Non-Aryl Nitrenium Ions and Their Rearrangements
    Falvey, Daniel E.
    ACS OMEGA, 2018, 3 (08): : 10418 - 10432
  • [6] THEORETICAL-STUDIES OF IMIDAZOLE NITRENIUM AND CARBENIUM IONS
    BOLTON, JL
    MCCLELLAND, RA
    THEOCHEM-JOURNAL OF MOLECULAR STRUCTURE, 1988, 42 (3-4): : 379 - 389
  • [7] Singlet and triplet states in the reactions of nitrenium ions
    Falvey, DE
    JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 1999, 12 (08) : 589 - 596
  • [8] HYDROCARBON IONS WITH TRIPLET GROUND STATES
    JESSE, RE
    BILOEN, P
    PRINS, R
    VANVOORST, JDW
    HOIJTINK, GJ
    MOLECULAR PHYSICS, 1963, 6 (06) : 633 - 635
  • [9] Structures of reactive nitrenium ions:: Time-resolved infrared laser flash photolysis and computational studies of substituted N-methyl-N-arylnitrenium ions
    Srivastava, S
    Ruane, PH
    Toscano, JP
    Sullivan, MB
    Cramer, CJ
    Chiapperino, D
    Reed, EC
    Falvey, DE
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (34) : 8271 - 8278
  • [10] Computational studies of benzyl-substituted halonium ions
    Haubenstock, H
    Sauers, RR
    TETRAHEDRON, 2005, 61 (35) : 8358 - 8365
1234