Tunneling control of chemical reactions: C-H insertion versus H-tunneling in tert-butylhydroxycarbene
dc.contributor.author | Ley, David | |
dc.contributor.author | Gerbig, Dennis | |
dc.contributor.author | Schreiner, Peter R. | |
dc.date.accessioned | 2023-06-02T13:37:37Z | |
dc.date.available | 2020-05-20T07:36:21Z | |
dc.date.available | 2023-06-02T13:37:37Z | |
dc.date.issued | 2013 | |
dc.description.abstract | Elusive tert-butylhydroxycarbene was generated in the gas phase via high-vacuum flash pyrolysis of tert-butylglyoxylic acid at 960 degrees C. The pyrolysis products were subsequently matrix isolated in solid Ar at 11 K and characterized by means of IR spectroscopy. While still being exposed to the harsh pyrolysis conditions, the hydroxycarbene undergoes CH-insertion to dimethylcyclopropanol, as well as a CC-insertion to novel methylbutenol, with activation barriers of 23.8 and 31.0 kcal mol(-1), respectively. Once embedded in the cold Ar matrix, the carbene transforms to its isomer pivaldehyde not only by photolysis, but it also cuts through the barrier of 27.3 kcal mol(-1) by quantum mechanical tunneling. The temperature independent half-life is measured as 1.7 h; the tunneling pathway was entirely blocked upon O-deuteration. The experimental half-life of tert-butylhydroxycarbene was verified by tunneling computations applying the Wentzel-Kramers-Brillouin formalism on the minimum energy path evaluated at the computationally feasible M06-2X/6-311++G(d,p) level of theory. Our experimental findings are supported by relative energy computations at the CCSD(T)/cc-pVDZ level of theory. | en |
dc.identifier.uri | http://nbn-resolving.de/urn:nbn:de:hebis:26-opus-151330 | |
dc.identifier.uri | https://jlupub.ub.uni-giessen.de//handle/jlupub/16365 | |
dc.identifier.uri | http://dx.doi.org/10.22029/jlupub-15745 | |
dc.language.iso | en | de_DE |
dc.rights | In Copyright | * |
dc.rights.uri | http://rightsstatements.org/page/InC/1.0/ | * |
dc.subject.ddc | ddc:540 | de_DE |
dc.title | Tunneling control of chemical reactions: C-H insertion versus H-tunneling in tert-butylhydroxycarbene | en |
dc.type | article | de_DE |
local.affiliation | FB 08 - Biologie und Chemie | de_DE |
local.comment | Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich. This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively. | |
local.opus.fachgebiet | Chemie | de_DE |
local.opus.id | 15133 | |
local.opus.institute | Institute of Organic Chemistry | de_DE |
local.source.freetext | Chemical Science 4, 677-684, doi: 10.1039/c2sc21555a | de_DE |
local.source.uri | https://doi.org/10.1039/c2sc21555a |
Dateien
Originalbündel
1 - 1 von 1
Lade...
- Name:
- 10.1039_c2sc21555a.pdf
- Größe:
- 570.34 KB
- Format:
- Adobe Portable Document Format