Toward product control in ring-opening oligomerization of 9H-9-borafluorenes
Copyright © 2014 Wiley Periodicals, Inc.
| Veröffentlicht in: | Journal of computational chemistry. - 1984. - 35(2014), 15 vom: 05. Juni, Seite 1107-10 |
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| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2014
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| Zugriff auf das übergeordnete Werk: | Journal of computational chemistry |
| Schlagworte: | Journal Article aromaticity boron ring-opening polymerization substituent effect |
| Zusammenfassung: | Copyright © 2014 Wiley Periodicals, Inc. To get deep insights into the structure-reactivity relationship for ring-opening oligomerization reactions toward targeted design of novel main-chain boron-containing materials, detailed DFT B97D/TZVP calculations are carried out to compare the ring-opening oligomerization of both unsubstituted and tert-butyl (tBu)-substituted 9H-9-borafluorenes. In contrast to substituent exchange between normal boranes, such reactions are initiated by substituent exchanges involving double B-C-B bridged intermediates. On tBu-substitution, the B-C-B, and B-H-B bridged dimer intermediate is stabilized mainly due to enhanced barrier of 18.1 kcal/mol toward further trimerization channel and higher isomerization barrier of 22.5 kcal/mol toward the double B-H-B bridged dimer. In good agreement with available experiments, it is clearly shown that various product channels can be efficiently controlled by bulky substitution and by reaction temperatures, pointing out the way toward desired higher oligomers with improved thermal stability |
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| Beschreibung: | Date Completed 15.04.2015 Date Revised 28.04.2014 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1096-987X |
| DOI: | 10.1002/jcc.23555 |