Bringing Homogeneous Iron Catalysts on the Heterogeneous Side: Solutions for Immobilization
Noble metal catalysts currently dominate the landscape of chemical synthesis, but cheaper and less toxic derivatives are recently emerging as more sustainable solutions. Iron is among the possible alternative metals due to its biocompatibility and exceptional versatility. Nowadays, iron catalysts wo...
| Main Authors: | , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2021-05-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/26/9/2728 |
| _version_ | 1797535179433050112 |
|---|---|
| author | Fabio Moccia Luca Rigamonti Alessandro Messori Valerio Zanotti Rita Mazzoni |
| author_facet | Fabio Moccia Luca Rigamonti Alessandro Messori Valerio Zanotti Rita Mazzoni |
| author_sort | Fabio Moccia |
| collection | DOAJ |
| description | Noble metal catalysts currently dominate the landscape of chemical synthesis, but cheaper and less toxic derivatives are recently emerging as more sustainable solutions. Iron is among the possible alternative metals due to its biocompatibility and exceptional versatility. Nowadays, iron catalysts work essentially in homogeneous conditions, while heterogeneous catalysts would be better performing and more desirable systems for a broad industrial application. In this review, approaches for heterogenization of iron catalysts reported in the literature within the last two decades are summarized, and utility and critical points are discussed. The immobilization on silica of <i>bis</i>(arylimine)pyridyl iron complexes, good catalysts in the polymerization of olefins, is the first useful heterogeneous strategy described. Microporous molecular sieves also proved to be good iron catalyst carriers, able to provide confined geometries where olefin polymerization can occur. Same immobilizing supports (e.g., MCM-41 and MCM-48) are suitable for anchoring iron-based catalysts for styrene, cyclohexene and cyclohexane oxidation. Another excellent example is the anchoring to a Merrifield resin of an Fe<sup>II</sup>-anthranilic acid complex, active in the catalytic reaction of urea with alcohols and amines for the synthesis of carbamates and <i>N</i>-substituted ureas, respectively. A SILP (Supported Ionic Liquid Phase) catalytic system has been successfully employed for the heterogenization of a chemoselective iron catalyst active in aldehyde hydrogenation. Finally, Fe<sup>III</sup> ions supported on polyvinylpyridine grafted chitosan made a useful heterogeneous catalytic system for C–H bond activation. |
| first_indexed | 2024-03-10T11:40:52Z |
| format | Article |
| id | doaj.art-deffa2f5792f4ffbb9eb8d18aa147689 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T11:40:52Z |
| publishDate | 2021-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-deffa2f5792f4ffbb9eb8d18aa1476892023-11-21T18:32:51ZengMDPI AGMolecules1420-30492021-05-01269272810.3390/molecules26092728Bringing Homogeneous Iron Catalysts on the Heterogeneous Side: Solutions for ImmobilizationFabio Moccia0Luca Rigamonti1Alessandro Messori2Valerio Zanotti3Rita Mazzoni4Dipartimento di Chimica Industriale “Toso Montanari”, Università degli Studi di Bologna, viale Risorgimento 4, 40136 Bologna, ItalyDipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Modena e Reggio Emilia, via G. Campi 103, 41125 Modena, ItalyDipartimento di Chimica Industriale “Toso Montanari”, Università degli Studi di Bologna, viale Risorgimento 4, 40136 Bologna, ItalyDipartimento di Chimica Industriale “Toso Montanari”, Università degli Studi di Bologna, viale Risorgimento 4, 40136 Bologna, ItalyDipartimento di Chimica Industriale “Toso Montanari”, Università degli Studi di Bologna, viale Risorgimento 4, 40136 Bologna, ItalyNoble metal catalysts currently dominate the landscape of chemical synthesis, but cheaper and less toxic derivatives are recently emerging as more sustainable solutions. Iron is among the possible alternative metals due to its biocompatibility and exceptional versatility. Nowadays, iron catalysts work essentially in homogeneous conditions, while heterogeneous catalysts would be better performing and more desirable systems for a broad industrial application. In this review, approaches for heterogenization of iron catalysts reported in the literature within the last two decades are summarized, and utility and critical points are discussed. The immobilization on silica of <i>bis</i>(arylimine)pyridyl iron complexes, good catalysts in the polymerization of olefins, is the first useful heterogeneous strategy described. Microporous molecular sieves also proved to be good iron catalyst carriers, able to provide confined geometries where olefin polymerization can occur. Same immobilizing supports (e.g., MCM-41 and MCM-48) are suitable for anchoring iron-based catalysts for styrene, cyclohexene and cyclohexane oxidation. Another excellent example is the anchoring to a Merrifield resin of an Fe<sup>II</sup>-anthranilic acid complex, active in the catalytic reaction of urea with alcohols and amines for the synthesis of carbamates and <i>N</i>-substituted ureas, respectively. A SILP (Supported Ionic Liquid Phase) catalytic system has been successfully employed for the heterogenization of a chemoselective iron catalyst active in aldehyde hydrogenation. Finally, Fe<sup>III</sup> ions supported on polyvinylpyridine grafted chitosan made a useful heterogeneous catalytic system for C–H bond activation.https://www.mdpi.com/1420-3049/26/9/2728iron catalystsolefin polymerizationhydrogen transferimmobilizationSILPMCM-41 |
| spellingShingle | Fabio Moccia Luca Rigamonti Alessandro Messori Valerio Zanotti Rita Mazzoni Bringing Homogeneous Iron Catalysts on the Heterogeneous Side: Solutions for Immobilization Molecules iron catalysts olefin polymerization hydrogen transfer immobilization SILP MCM-41 |
| title | Bringing Homogeneous Iron Catalysts on the Heterogeneous Side: Solutions for Immobilization |
| title_full | Bringing Homogeneous Iron Catalysts on the Heterogeneous Side: Solutions for Immobilization |
| title_fullStr | Bringing Homogeneous Iron Catalysts on the Heterogeneous Side: Solutions for Immobilization |
| title_full_unstemmed | Bringing Homogeneous Iron Catalysts on the Heterogeneous Side: Solutions for Immobilization |
| title_short | Bringing Homogeneous Iron Catalysts on the Heterogeneous Side: Solutions for Immobilization |
| title_sort | bringing homogeneous iron catalysts on the heterogeneous side solutions for immobilization |
| topic | iron catalysts olefin polymerization hydrogen transfer immobilization SILP MCM-41 |
| url | https://www.mdpi.com/1420-3049/26/9/2728 |
| work_keys_str_mv | AT fabiomoccia bringinghomogeneousironcatalystsontheheterogeneoussidesolutionsforimmobilization AT lucarigamonti bringinghomogeneousironcatalystsontheheterogeneoussidesolutionsforimmobilization AT alessandromessori bringinghomogeneousironcatalystsontheheterogeneoussidesolutionsforimmobilization AT valeriozanotti bringinghomogeneousironcatalystsontheheterogeneoussidesolutionsforimmobilization AT ritamazzoni bringinghomogeneousironcatalystsontheheterogeneoussidesolutionsforimmobilization |