Theoretical investigations of the reactivities of four-membered N-heterocyclic carbene analogues of the group 13 elements
2011 Wiley Periodicals, Inc.
| Veröffentlicht in: | Journal of computational chemistry. - 1984. - 33(2012), 1 vom: 05. Jan., Seite 103-11 |
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| Format: | Online-Aufsatz |
| Sprache: | English |
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2012
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| Zugriff auf das übergeordnete Werk: | Journal of computational chemistry |
| Schlagworte: | Journal Article Heterocyclic Compounds Metals, Heavy Organometallic Compounds carbene 2465-56-7 Methane OP0UW79H66 |
| Zusammenfassung: | 2011 Wiley Periodicals, Inc. The potential energy surfaces for the chemical reactions of four-membered N-heterocyclic group 13 heavy carbeneoid species have been studied using density functional theory (Becke, 3-parameter, Lee-Yang-Parr (B3LYP)/Los Alamos National Laboratory 2-Double-Zeta (LANL2DZ)). Five four-membered group 13 heavy carbeneoid species, iPr2NC(NAr)2E:, where E ¼ B, Al, Ga, In, and Tl, have been chosen as model reactants in this work. Also, three kinds of chemical reactions, CAH bond insertion, alkene cycloaddition, and dimerization, have been used to study the chemical reactivities of these group 13 fourmembered N-heterocyclic carbeneoid species. In principle, our present theoretical work predicts that the larger the ffNEN bond angle of the four-membered group 13 iPr2NC(NAr)2E: species, the smaller the singlet–triplet splitting, the lower the activation barrier, and, in turn, the more rapid its chemical reactions to various chemical species. Moreover, our theoretical investigations suggest that the relative carbenic reactivity decreases in the following order: B > Al > Ga > In > Tl. That is, the heavier the group 13 atom (E), the more stable its fourmembered carbeneoid toward chemical reactions is. As a result, our computations predict that the four-membered heavy group 13 iPr2NC(NAr)2E: species (E ¼ Al, Ga, In, and Tl) should be both kinetically and thermodynamically stable, and can be readily synthesized and isolated at room temperature. Furthermore, the singlet–triplet energy splitting of the four-membered group 13 iPr2NC(NAr)2E: species, as described in the configuration mixing model attributed to the work of Pross and Shaik, can be used as a diagnostic tool to predict their reactivities. The results obtained allow a number of predictions to be made |
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| Beschreibung: | Date Completed 04.06.2012 Date Revised 27.10.2019 published: Print Citation Status MEDLINE |
| ISSN: | 1096-987X |