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Article: Stable group 8 metal porphyrin mono- and bis(dialkylcarbene) complexes: synthesis, characterization, and catalytic activity
Title | Stable group 8 metal porphyrin mono- and bis(dialkylcarbene) complexes: synthesis, characterization, and catalytic activity |
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Authors | |
Keywords | Catalyst activity Chemical stability Electronic structure Iron compounds Metal ions |
Issue Date | 2020 |
Publisher | Royal Society of Chemistry: Open Access. The Journal's web site is located at http://www.rsc.org/publishing/journals/sc/About.asp |
Citation | Chemical Science, 2020, v. 11 n. 8, p. 2243-2259 How to Cite? |
Abstract | Alkyl-substituted carbene (CHR or CR2, R = alkyl) complexes have been extensively studied for alkylcarbene (CHR) ligands coordinated with high-valent early transition metal ions (a.k.a. Schrock carbenes or alkylidenes), yet dialkylcarbene (CR2) complexes remain less developed with bis(dialkylcarbene) species being little (if at all) explored. Herein, several group 8 metal porphyrin dialkylcarbene complexes, including Fe- and Ru-mono(dialkylcarbene) complexes [M(Por)(Ad)] (1a,b, M = Fe, Por = porphyrinato dianion, Ad = 2-adamantylidene; 2a,b, M = Ru) and Os-bis(dialkylcarbene) complexes [Os(Por)(Ad)2] (3a–c), are synthesized and crystallographically characterized. Detailed investigations into their electronic structures reveal that these complexes are formally low-valent M(II)-carbene in nature. These complexes display remarkable thermal stability and chemical inertness, which are rationalized by a synergistic effect of strong metal-carbene covalency, hyperconjugation, and a rigid diamondoid carbene skeleton. Various spectroscopic techniques and DFT calculations suggest that the dialkylcarbene Ad ligand is unique compared to other common carbene ligands as it acts as both a potent σ-donor and π-acceptor; its unique electronic and structural features, together with the steric effect of the porphyrin macrocycle, make its Fe porphyrin complex 1a an active and robust catalyst for intermolecular diarylcarbene transfer reactions including cyclopropanation (up to 90% yield) and X–H (X = S, N, O, C) insertion (up to 99% yield) reactions. |
Persistent Identifier | http://hdl.handle.net/10722/282891 |
ISSN | 2023 Impact Factor: 7.6 2023 SCImago Journal Rankings: 2.333 |
ISI Accession Number ID | |
Errata |
DC Field | Value | Language |
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dc.contributor.author | Wang, HX | - |
dc.contributor.author | Wan, Q | - |
dc.contributor.author | Low, KH | - |
dc.contributor.author | Zhou, CY | - |
dc.contributor.author | Huang, JS | - |
dc.contributor.author | Zhang, JL | - |
dc.contributor.author | Che, CM | - |
dc.date.accessioned | 2020-06-05T06:22:47Z | - |
dc.date.available | 2020-06-05T06:22:47Z | - |
dc.date.issued | 2020 | - |
dc.identifier.citation | Chemical Science, 2020, v. 11 n. 8, p. 2243-2259 | - |
dc.identifier.issn | 2041-6520 | - |
dc.identifier.uri | http://hdl.handle.net/10722/282891 | - |
dc.description.abstract | Alkyl-substituted carbene (CHR or CR2, R = alkyl) complexes have been extensively studied for alkylcarbene (CHR) ligands coordinated with high-valent early transition metal ions (a.k.a. Schrock carbenes or alkylidenes), yet dialkylcarbene (CR2) complexes remain less developed with bis(dialkylcarbene) species being little (if at all) explored. Herein, several group 8 metal porphyrin dialkylcarbene complexes, including Fe- and Ru-mono(dialkylcarbene) complexes [M(Por)(Ad)] (1a,b, M = Fe, Por = porphyrinato dianion, Ad = 2-adamantylidene; 2a,b, M = Ru) and Os-bis(dialkylcarbene) complexes [Os(Por)(Ad)2] (3a–c), are synthesized and crystallographically characterized. Detailed investigations into their electronic structures reveal that these complexes are formally low-valent M(II)-carbene in nature. These complexes display remarkable thermal stability and chemical inertness, which are rationalized by a synergistic effect of strong metal-carbene covalency, hyperconjugation, and a rigid diamondoid carbene skeleton. Various spectroscopic techniques and DFT calculations suggest that the dialkylcarbene Ad ligand is unique compared to other common carbene ligands as it acts as both a potent σ-donor and π-acceptor; its unique electronic and structural features, together with the steric effect of the porphyrin macrocycle, make its Fe porphyrin complex 1a an active and robust catalyst for intermolecular diarylcarbene transfer reactions including cyclopropanation (up to 90% yield) and X–H (X = S, N, O, C) insertion (up to 99% yield) reactions. | - |
dc.language | eng | - |
dc.publisher | Royal Society of Chemistry: Open Access. The Journal's web site is located at http://www.rsc.org/publishing/journals/sc/About.asp | - |
dc.relation.ispartof | Chemical Science | - |
dc.rights | This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License. | - |
dc.subject | Catalyst activity | - |
dc.subject | Chemical stability | - |
dc.subject | Electronic structure | - |
dc.subject | Iron compounds | - |
dc.subject | Metal ions | - |
dc.title | Stable group 8 metal porphyrin mono- and bis(dialkylcarbene) complexes: synthesis, characterization, and catalytic activity | - |
dc.type | Article | - |
dc.identifier.email | Wang, HX: wanghx1@hku.hk | - |
dc.identifier.email | Wan, Q: wendyqyw@hku.hk | - |
dc.identifier.email | Low, KH: khlow@hku.hk | - |
dc.identifier.email | Zhou, CY: cyzhou@hku.hk | - |
dc.identifier.email | Huang, JS: jshuang@hku.hk | - |
dc.identifier.email | Che, CM: chemhead@hku.hk | - |
dc.identifier.authority | Zhou, CY=rp00843 | - |
dc.identifier.authority | Huang, JS=rp00709 | - |
dc.identifier.authority | Che, CM=rp00670 | - |
dc.description.nature | published_or_final_version | - |
dc.identifier.doi | 10.1039/C9SC05432D | - |
dc.identifier.scopus | eid_2-s2.0-85080856923 | - |
dc.identifier.hkuros | 310318 | - |
dc.identifier.volume | 11 | - |
dc.identifier.issue | 8 | - |
dc.identifier.spage | 2243 | - |
dc.identifier.epage | 2259 | - |
dc.identifier.isi | WOS:000518011700023 | - |
dc.publisher.place | United Kingdom | - |
dc.relation.erratum | doi:10.1039/d0sc90103b | - |
dc.relation.erratum | eid:eid_2-s2.0-85086429359 | - |
dc.identifier.issnl | 2041-6520 | - |