Thermal rearrangements of Berson TMMs have been investigated. For this purpose, the potential
energy surface of the singlet S state has been explored to test Benson&rsquo / s Schemes 1-2
(Figure 1.10 and 1.11). It is verified that the enyne 9c plays a central role in connecting the
two portions of the reaction path (Berson Schemes 1 and 2). Connectivity of successive minima
on a given surface has been verified by intrinsic reaction coordinate (IRC) computations.
Density functional theory (DFT) and multiconfiguration self consistent field (MCSCF) methods
have been employed for these purposes. Further, single point coupled-cluster singles and
doubles with perturbative triples (CCSD(T)) energy computations have been carried out at optimized
DFT or MCSCF geometries. All transition states (TS) connecting each neighboring
minimum have been located in the proposed mechanisms. It is concluded that the proposed
mechanisms are confirmed by the theoretical calculations. The computed activation energy
and enthalpy of reaction values are in good agreement with the available experimental values,
only differing by a few kcal mol-1.
| Identifer | oai:union.ndltd.org:METU/oai:etd.lib.metu.edu.tr:http://etd.lib.metu.edu.tr/upload/12613301/index.pdf |
| Date | 01 June 2011 |
| Creators | Bozkaya, Ugur |
| Contributors | Ozkan, Ilker |
| Publisher | METU |
| Source Sets | Middle East Technical Univ. |
| Language | English |
| Detected Language | English |
| Type | Ph.D. Thesis |
| Format | text/pdf |
| Rights | To liberate the content for METU campus |
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