Knorr, Johannes and Sokkar, Pandian and Costa, Paolo and Sander, Wolfram and Sanchez-Garcia, Elsa and Nuernberger, Patrick (2019) How Protic Solvents Determine the Reaction Mechanisms of Diphenylcarbene in Solution. JOURNAL OF ORGANIC CHEMISTRY, 84 (18). pp. 11450-11457. ISSN 0022-3263, 1520-6904
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We investigate the effects of small admixtures of protic solvent molecules, such as water and alcohols, on the ultrafast dynamics of diphenylcarbene in acetonitrile at room temperature. Broadband transient absorption measurements and quantum mechanics/molecular mechanics molecular dynamics simulations allow elucidating the dominant reaction mechanism of an intermediate hydrogen-bonded complex between singlet diphenylcarbene and a protic solvent molecule, thus competing with intersystem crossing. Analysis of the data indicates that complex formation is a diffusion-controlled process with orientational requirements. The reaction path involving a benzhydryl cation is less likely in neat bulkier alcohols, as it requires the interaction of the carbene with a protic solvent molecule being part of a hydrogen-bonded network. The simulations indicate a further reaction path toward O-H insertion and two side reactions depending on the involved protic solvent species. Thus, we established that not only the number but also the chemical nature of the protic solvent molecule determine which reaction path is pursued.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | EXCITED TRIPLET DIPHENYLCARBENE; GENERAL FORCE-FIELD; DIFFUSION-CONTROLLED REACTION; AUXILIARY BASIS-SETS; PICOSECOND LASER; MOLECULAR-DYNAMICS; SINGLET; INTERCONVERSION; PHOTOCHEMISTRY; AUTOMATION; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Physical Chemistry I > Prof. Dr. Patrick Nürnberger |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 30 Mar 2020 06:55 |
| Last Modified: | 06 Apr 2020 06:32 |
| URI: | https://pred.uni-regensburg.de/id/eprint/26232 |
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