Effect of Substituents of Cerium Pyrazolates and Pyrrolates on Carbon Dioxide Activation
Homoleptic ceric pyrazolates (pz) Ce(RR’pz)<sub>4</sub> (R = R’ = <i>t</i>Bu; R = R’ = Ph; R = <i>t</i>Bu, R’ = Me) were synthesized by the protonolysis reaction of Ce[N(SiHMe<sub>2</sub>)<sub>2</sub>]<sub>4</sub> with the corre...
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MDPI AG
2021-03-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/26/7/1957 |
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| author | Uwe Bayer Adrian Jenner Jonas Riedmaier Cäcilia Maichle-Mössmer Reiner Anwander |
| author_facet | Uwe Bayer Adrian Jenner Jonas Riedmaier Cäcilia Maichle-Mössmer Reiner Anwander |
| author_sort | Uwe Bayer |
| collection | DOAJ |
| description | Homoleptic ceric pyrazolates (pz) Ce(RR’pz)<sub>4</sub> (R = R’ = <i>t</i>Bu; R = R’ = Ph; R = <i>t</i>Bu, R’ = Me) were synthesized by the protonolysis reaction of Ce[N(SiHMe<sub>2</sub>)<sub>2</sub>]<sub>4</sub> with the corresponding pyrazole derivative. The resulting complexes were investigated in their reactivity toward CO<sub>2</sub>, revealing a significant influence of the bulkiness of the substituents on the pyrazolato ligands. The efficiency of the CO<sub>2</sub> insertion was found to increase in the order of <i>t</i>Bu<sub>2</sub>pz < Ph<sub>2</sub>pz < <i>t</i>BuMepz < Me<sub>2</sub>pz. For comparison, the pyrrole-based ate complexes [Ce<sub>2</sub>(pyr)<sub>6</sub>(<i>µ</i>-pyr)<sub>2</sub>(thf)<sub>2</sub>][Li(thf)<sub>4</sub>]<sub>2</sub> (pyr = pyrrolato) and [Ce(cbz)<sub>4</sub>(thf)<sub>2</sub>][Li(thf)<sub>4</sub>] (cbz = carbazolato) were obtained via protonolysis of the cerous ate complex Ce[N(SiHMe<sub>2</sub>)<sub>2</sub>]<sub>4</sub>Li(thf) with pyrrole and carbazole, respectively. Treatment of the pyrrolate/carbazolate complexes with CO<sub>2</sub> seemed promising, but any reversibility could not be observed. |
| first_indexed | 2024-03-10T12:45:44Z |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T12:45:44Z |
| publishDate | 2021-03-01 |
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| record_format | Article |
| series | Molecules |
| spelling | doaj.art-a8f261d29c48423f8964533eded44d4e2023-11-21T13:31:37ZengMDPI AGMolecules1420-30492021-03-01267195710.3390/molecules26071957Effect of Substituents of Cerium Pyrazolates and Pyrrolates on Carbon Dioxide ActivationUwe Bayer0Adrian Jenner1Jonas Riedmaier2Cäcilia Maichle-Mössmer3Reiner Anwander4Institute of Inorganic Chemistry, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, GermanyInstitute of Inorganic Chemistry, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, GermanyInstitute of Inorganic Chemistry, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, GermanyInstitute of Inorganic Chemistry, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, GermanyInstitute of Inorganic Chemistry, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, GermanyHomoleptic ceric pyrazolates (pz) Ce(RR’pz)<sub>4</sub> (R = R’ = <i>t</i>Bu; R = R’ = Ph; R = <i>t</i>Bu, R’ = Me) were synthesized by the protonolysis reaction of Ce[N(SiHMe<sub>2</sub>)<sub>2</sub>]<sub>4</sub> with the corresponding pyrazole derivative. The resulting complexes were investigated in their reactivity toward CO<sub>2</sub>, revealing a significant influence of the bulkiness of the substituents on the pyrazolato ligands. The efficiency of the CO<sub>2</sub> insertion was found to increase in the order of <i>t</i>Bu<sub>2</sub>pz < Ph<sub>2</sub>pz < <i>t</i>BuMepz < Me<sub>2</sub>pz. For comparison, the pyrrole-based ate complexes [Ce<sub>2</sub>(pyr)<sub>6</sub>(<i>µ</i>-pyr)<sub>2</sub>(thf)<sub>2</sub>][Li(thf)<sub>4</sub>]<sub>2</sub> (pyr = pyrrolato) and [Ce(cbz)<sub>4</sub>(thf)<sub>2</sub>][Li(thf)<sub>4</sub>] (cbz = carbazolato) were obtained via protonolysis of the cerous ate complex Ce[N(SiHMe<sub>2</sub>)<sub>2</sub>]<sub>4</sub>Li(thf) with pyrrole and carbazole, respectively. Treatment of the pyrrolate/carbazolate complexes with CO<sub>2</sub> seemed promising, but any reversibility could not be observed.https://www.mdpi.com/1420-3049/26/7/1957ceriumpyrazolespyrrolescarbazolescarbon dioxide |
| spellingShingle | Uwe Bayer Adrian Jenner Jonas Riedmaier Cäcilia Maichle-Mössmer Reiner Anwander Effect of Substituents of Cerium Pyrazolates and Pyrrolates on Carbon Dioxide Activation Molecules cerium pyrazoles pyrroles carbazoles carbon dioxide |
| title | Effect of Substituents of Cerium Pyrazolates and Pyrrolates on Carbon Dioxide Activation |
| title_full | Effect of Substituents of Cerium Pyrazolates and Pyrrolates on Carbon Dioxide Activation |
| title_fullStr | Effect of Substituents of Cerium Pyrazolates and Pyrrolates on Carbon Dioxide Activation |
| title_full_unstemmed | Effect of Substituents of Cerium Pyrazolates and Pyrrolates on Carbon Dioxide Activation |
| title_short | Effect of Substituents of Cerium Pyrazolates and Pyrrolates on Carbon Dioxide Activation |
| title_sort | effect of substituents of cerium pyrazolates and pyrrolates on carbon dioxide activation |
| topic | cerium pyrazoles pyrroles carbazoles carbon dioxide |
| url | https://www.mdpi.com/1420-3049/26/7/1957 |
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