The effects of substituents on the reductive elimination of difluoromethylated hydrazones from small bite-angle PdII molecular catalyst: A DFT study
<p dir="ltr">We report herein computational insights concerning the electronic effects of the substituents on the reductive elimination of difluoroalkylated hydrazones from a small bite-angle PdII molecular catalyst. The DFT results revealed that hydrazones with substituted electron-...
محفوظ في:
| المؤلف الرئيسي: | |
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| مؤلفون آخرون: | , |
| منشور في: |
2021
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| الموضوعات: | |
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| _version_ | 1864513538041577472 |
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| author | Abdulilah Dawoud Bani-Yaseen (16932528) |
| author2 | Rahma Sarayrah (16932531) Fania Nabilla (16932534) |
| author2_role | author author |
| author_facet | Abdulilah Dawoud Bani-Yaseen (16932528) Rahma Sarayrah (16932531) Fania Nabilla (16932534) |
| author_role | author |
| dc.creator.none.fl_str_mv | Abdulilah Dawoud Bani-Yaseen (16932528) Rahma Sarayrah (16932531) Fania Nabilla (16932534) |
| dc.date.none.fl_str_mv | 2021-03-01T00:00:00Z |
| dc.identifier.none.fl_str_mv | 10.1016/j.comptc.2021.113162 |
| dc.relation.none.fl_str_mv | https://figshare.com/articles/journal_contribution/The_effects_of_substituents_on_the_reductive_elimination_of_difluoromethylated_hydrazones_from_small_bite-angle_PdII_molecular_catalyst_A_DFT_study/24083685 |
| dc.rights.none.fl_str_mv | CC BY 4.0 info:eu-repo/semantics/openAccess |
| dc.subject.none.fl_str_mv | Chemical sciences Physical chemistry Theoretical and computational chemistry Difluoromethylation Palladium Reductive elimination Energy barrier Density functional calculations |
| dc.title.none.fl_str_mv | The effects of substituents on the reductive elimination of difluoromethylated hydrazones from small bite-angle PdII molecular catalyst: A DFT study |
| dc.type.none.fl_str_mv | Text Journal contribution info:eu-repo/semantics/publishedVersion text contribution to journal |
| description | <p dir="ltr">We report herein computational insights concerning the electronic effects of the substituents on the reductive elimination of difluoroalkylated hydrazones from a small bite-angle PdII molecular catalyst. The DFT results revealed that hydrazones with substituted electron-withdrawing (EW) groups (e.g. p-NO<sub>2</sub>) can notably exhibit a depreciation in the activation energy barrier (ΔG‡ ). According to the DFT-calculated ΔG‡ , the Hammett analysis revealed an excellent correlation (R2 = 0.98) with a reaction constant (ρ) of + 2.34 indicative of an enhanced accumulation of negative charge density at the transition state (TS). Natural bond orbital (NBO) charge analysis of the corresponding TS suggests distinguishable nucleophilic and electrophilic characteristics for selected atoms at the reaction center. Hence, the NBO analysis revealed an electronic transition of the type lp(C<sub>1</sub>) → σ*(PdII-C<sub>2</sub>) for EW = NO<sub>2</sub> with stabilizing energy E(2) of 143 kcal/mol indicative of more stabilized TS that is well in line with the ΔG‡ and NBO analyses.</p><h2>Other Information</h2><p dir="ltr">Published in: Computational and Theoretical Chemistry<br>License: <a href="http://creativecommons.org/licenses/by/4.0/" target="_blank">http://creativecommons.org/licenses/by/4.0/</a><br>See article on publisher's website: <a href="https://dx.doi.org/10.1016/j.comptc.2021.113162" target="_blank">https://dx.doi.org/10.1016/j.comptc.2021.113162</a></p> |
| eu_rights_str_mv | openAccess |
| id | Manara2_fb879c1d19391a37236b87d6b7e84ede |
| identifier_str_mv | 10.1016/j.comptc.2021.113162 |
| network_acronym_str | Manara2 |
| network_name_str | Manara2 |
| oai_identifier_str | oai:figshare.com:article/24083685 |
| publishDate | 2021 |
| repository.mail.fl_str_mv | |
| repository.name.fl_str_mv | |
| repository_id_str | |
| rights_invalid_str_mv | CC BY 4.0 |
| spelling | The effects of substituents on the reductive elimination of difluoromethylated hydrazones from small bite-angle PdII molecular catalyst: A DFT studyAbdulilah Dawoud Bani-Yaseen (16932528)Rahma Sarayrah (16932531)Fania Nabilla (16932534)Chemical sciencesPhysical chemistryTheoretical and computational chemistryDifluoromethylationPalladiumReductive eliminationEnergy barrierDensity functional calculations<p dir="ltr">We report herein computational insights concerning the electronic effects of the substituents on the reductive elimination of difluoroalkylated hydrazones from a small bite-angle PdII molecular catalyst. The DFT results revealed that hydrazones with substituted electron-withdrawing (EW) groups (e.g. p-NO<sub>2</sub>) can notably exhibit a depreciation in the activation energy barrier (ΔG‡ ). According to the DFT-calculated ΔG‡ , the Hammett analysis revealed an excellent correlation (R2 = 0.98) with a reaction constant (ρ) of + 2.34 indicative of an enhanced accumulation of negative charge density at the transition state (TS). Natural bond orbital (NBO) charge analysis of the corresponding TS suggests distinguishable nucleophilic and electrophilic characteristics for selected atoms at the reaction center. Hence, the NBO analysis revealed an electronic transition of the type lp(C<sub>1</sub>) → σ*(PdII-C<sub>2</sub>) for EW = NO<sub>2</sub> with stabilizing energy E(2) of 143 kcal/mol indicative of more stabilized TS that is well in line with the ΔG‡ and NBO analyses.</p><h2>Other Information</h2><p dir="ltr">Published in: Computational and Theoretical Chemistry<br>License: <a href="http://creativecommons.org/licenses/by/4.0/" target="_blank">http://creativecommons.org/licenses/by/4.0/</a><br>See article on publisher's website: <a href="https://dx.doi.org/10.1016/j.comptc.2021.113162" target="_blank">https://dx.doi.org/10.1016/j.comptc.2021.113162</a></p>2021-03-01T00:00:00ZTextJournal contributioninfo:eu-repo/semantics/publishedVersiontextcontribution to journal10.1016/j.comptc.2021.113162https://figshare.com/articles/journal_contribution/The_effects_of_substituents_on_the_reductive_elimination_of_difluoromethylated_hydrazones_from_small_bite-angle_PdII_molecular_catalyst_A_DFT_study/24083685CC BY 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/240836852021-03-01T00:00:00Z |
| spellingShingle | The effects of substituents on the reductive elimination of difluoromethylated hydrazones from small bite-angle PdII molecular catalyst: A DFT study Abdulilah Dawoud Bani-Yaseen (16932528) Chemical sciences Physical chemistry Theoretical and computational chemistry Difluoromethylation Palladium Reductive elimination Energy barrier Density functional calculations |
| status_str | publishedVersion |
| title | The effects of substituents on the reductive elimination of difluoromethylated hydrazones from small bite-angle PdII molecular catalyst: A DFT study |
| title_full | The effects of substituents on the reductive elimination of difluoromethylated hydrazones from small bite-angle PdII molecular catalyst: A DFT study |
| title_fullStr | The effects of substituents on the reductive elimination of difluoromethylated hydrazones from small bite-angle PdII molecular catalyst: A DFT study |
| title_full_unstemmed | The effects of substituents on the reductive elimination of difluoromethylated hydrazones from small bite-angle PdII molecular catalyst: A DFT study |
| title_short | The effects of substituents on the reductive elimination of difluoromethylated hydrazones from small bite-angle PdII molecular catalyst: A DFT study |
| title_sort | The effects of substituents on the reductive elimination of difluoromethylated hydrazones from small bite-angle PdII molecular catalyst: A DFT study |
| topic | Chemical sciences Physical chemistry Theoretical and computational chemistry Difluoromethylation Palladium Reductive elimination Energy barrier Density functional calculations |