A Computational Approach to Structure and Reactivity of Boron Containing Reactive Intermediates

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dc.contributor.advisor Bettinger, Holger F. (Prof. Dr.)
dc.contributor.author Krasowska, Małgorzata
dc.date.accessioned 2017-01-13T13:24:28Z
dc.date.available 2017-01-13T13:24:28Z
dc.date.issued 2016-01-13
dc.identifier.other 481749969 de_DE
dc.identifier.uri http://hdl.handle.net/10900/73951
dc.identifier.uri http://nbn-resolving.de/urn:nbn:de:bsz:21-dspace-739518 de_DE
dc.identifier.uri http://dx.doi.org/10.15496/publikation-15357
dc.description.abstract Computational chemistry methods were employed to study small boron containing reactive intermediates, such as borylenes, which are the analogs of carbenes and nitrenes, and borirenes and boriranes that are isoelectronic to cyclopropenyl and cyclopropyl cations, respectively. Density functional theory (DFT) was used to study the electronic and molecular structure of various substituted borylenes BR. The influence of substitution on the frontier molecular orbitals (FMO) energies, HOMO-LUMO energy gaps, and singlet-triplet energy splittings was also examined. In addition, two lowest singlet-singlet electronic transitions were computed using equation-of-motion coupled cluster singles and doubles (EOM-CCSD) and time-dependent density functional theory (TD-DFT). The reactivity of singlet borylenes towards unsaturated and saturated hydrocarbons was investigated. To study the mechanisms of the addition and insertion reactions, ethyne, ethene, and methane were chosen as model hydrocarbons. The philicity of borylenes was also studied in terms of geometrical parameters of the transition states calculated for the addition reactions. The aforementioned addition and insertion reactions involve weakly bound van der Waals complexes formed between hydrocarbons and borylenes that correspond to shallow minima on the potential energy surfaces. Spin-component scaled second-order Møller-Plesset perturbation theory (SCS-MP2) was used to study all complexes. Symmetry-adapted perturbation theory (SAPT) analysis was performed to study the nature of the interaction in borylene-hydrocarbon van der Waals complexes. The reactions of three-membered boron heterocycles (borirane and borirene) towards unsaturated hydrocarbons (ethyne and ethene) were investigated. Dimerization reactions of borirenes and boriranes were also studied using DFT and CCSD(T) methods. en
dc.language.iso en de_DE
dc.publisher Universität Tübingen de_DE
dc.publisher Universität Tübingen de_DE
dc.rights ubt-podok de_DE
dc.rights.uri http://tobias-lib.uni-tuebingen.de/doku/lic_mit_pod.php?la=de de_DE
dc.rights.uri http://tobias-lib.uni-tuebingen.de/doku/lic_mit_pod.php?la=en en
dc.subject.classification Bor de_DE
dc.subject.ddc 540 de_DE
dc.subject.other computational chemistry en
dc.subject.other boron en
dc.subject.other Computerchemie de_DE
dc.subject.other Borylene de_DE
dc.title A Computational Approach to Structure and Reactivity of Boron Containing Reactive Intermediates en
dc.type PhDThesis de_DE
dcterms.dateAccepted 2016-06-28
utue.publikation.fachbereich Chemie de_DE
utue.publikation.fakultaet 7 Mathematisch-Naturwissenschaftliche Fakultät de_DE

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