Insights into the Fluxional Processes of Monomethylcyclohexenyl Manganese Tricarbonyl
Multiple fluxional processes of 6-monomethylcyclohexenylmanganese tricarbonyl [(6-MeC<sub>6</sub>H<sub>8</sub>)Mn(CO)<sub>3</sub>, complex <b>1</b>] and 5-monomethylcyclohexenylmanganese tricarbonyl [(5-MeC<sub>6</sub>H<sub>8</sub&...
| Main Authors: | , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2023-04-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/28/7/3232 |
| _version_ | 1797607365379358720 |
|---|---|
| author | Guangchao Liang Min Zhang |
| author_facet | Guangchao Liang Min Zhang |
| author_sort | Guangchao Liang |
| collection | DOAJ |
| description | Multiple fluxional processes of 6-monomethylcyclohexenylmanganese tricarbonyl [(6-MeC<sub>6</sub>H<sub>8</sub>)Mn(CO)<sub>3</sub>, complex <b>1</b>] and 5-monomethylcyclohexenylmanganese tricarbonyl [(5-MeC<sub>6</sub>H<sub>8</sub>)Mn(CO)<sub>3</sub>, complex <b>2</b>] have been explored using density functional theory (DFT) computations. The contributions of four agostomers—<b>1</b>, <b>2</b>, <b>3,</b> and <b>4</b>—to the (MeC<sub>6</sub>H<sub>8</sub>)Mn(CO)<sub>3</sub> exchange processes were revealed. The computational results demonstrated that the 1, 2-agostic isomerization only occurred via the η<sup>4</sup>-diene hydride transition state (<b>TS-1-2</b>, 14.0 kcal/mol), which is consistent with the experimentally proposed high-energy exchange process (16.0 kcal/mol). Excellent agreement is observed (R<sup>2</sup> = 0.9862) when comparing the computed and experimentally observed variable temperature <sup>1</sup>H NMR chemical shifts. With these results, important insights into the role of agostic interaction in the homogeneous catalysis process could be made, especially with regard to transition metal catalyzed C-H activation. |
| first_indexed | 2024-03-11T05:30:03Z |
| format | Article |
| id | doaj.art-be7202a603b04a8480fe2f0ee2655d96 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T05:30:03Z |
| publishDate | 2023-04-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-be7202a603b04a8480fe2f0ee2655d962023-11-17T17:15:29ZengMDPI AGMolecules1420-30492023-04-01287323210.3390/molecules28073232Insights into the Fluxional Processes of Monomethylcyclohexenyl Manganese TricarbonylGuangchao Liang0Min Zhang1Academy of Advanced Interdisciplinary Research, Xidian University, Xi’an 710071, ChinaDepartment of Pharmacy, School of Medicine, Xi’an International University, Xi’an 710077, ChinaMultiple fluxional processes of 6-monomethylcyclohexenylmanganese tricarbonyl [(6-MeC<sub>6</sub>H<sub>8</sub>)Mn(CO)<sub>3</sub>, complex <b>1</b>] and 5-monomethylcyclohexenylmanganese tricarbonyl [(5-MeC<sub>6</sub>H<sub>8</sub>)Mn(CO)<sub>3</sub>, complex <b>2</b>] have been explored using density functional theory (DFT) computations. The contributions of four agostomers—<b>1</b>, <b>2</b>, <b>3,</b> and <b>4</b>—to the (MeC<sub>6</sub>H<sub>8</sub>)Mn(CO)<sub>3</sub> exchange processes were revealed. The computational results demonstrated that the 1, 2-agostic isomerization only occurred via the η<sup>4</sup>-diene hydride transition state (<b>TS-1-2</b>, 14.0 kcal/mol), which is consistent with the experimentally proposed high-energy exchange process (16.0 kcal/mol). Excellent agreement is observed (R<sup>2</sup> = 0.9862) when comparing the computed and experimentally observed variable temperature <sup>1</sup>H NMR chemical shifts. With these results, important insights into the role of agostic interaction in the homogeneous catalysis process could be made, especially with regard to transition metal catalyzed C-H activation.https://www.mdpi.com/1420-3049/28/7/3232agostic interactionfluxionalityVT-NMRdensity functional theory |
| spellingShingle | Guangchao Liang Min Zhang Insights into the Fluxional Processes of Monomethylcyclohexenyl Manganese Tricarbonyl Molecules agostic interaction fluxionality VT-NMR density functional theory |
| title | Insights into the Fluxional Processes of Monomethylcyclohexenyl Manganese Tricarbonyl |
| title_full | Insights into the Fluxional Processes of Monomethylcyclohexenyl Manganese Tricarbonyl |
| title_fullStr | Insights into the Fluxional Processes of Monomethylcyclohexenyl Manganese Tricarbonyl |
| title_full_unstemmed | Insights into the Fluxional Processes of Monomethylcyclohexenyl Manganese Tricarbonyl |
| title_short | Insights into the Fluxional Processes of Monomethylcyclohexenyl Manganese Tricarbonyl |
| title_sort | insights into the fluxional processes of monomethylcyclohexenyl manganese tricarbonyl |
| topic | agostic interaction fluxionality VT-NMR density functional theory |
| url | https://www.mdpi.com/1420-3049/28/7/3232 |
| work_keys_str_mv | AT guangchaoliang insightsintothefluxionalprocessesofmonomethylcyclohexenylmanganesetricarbonyl AT minzhang insightsintothefluxionalprocessesofmonomethylcyclohexenylmanganesetricarbonyl |