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Article: Stable group 8 metal porphyrin mono- and bis(dialkylcarbene) complexes: synthesis, characterization, and catalytic activity

TitleStable group 8 metal porphyrin mono- and bis(dialkylcarbene) complexes: synthesis, characterization, and catalytic activity
Authors
KeywordsCatalyst activity
Chemical stability
Electronic structure
Iron compounds
Metal ions
Issue Date2020
PublisherRoyal 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?
AbstractAlkyl-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 Identifierhttp://hdl.handle.net/10722/282891
ISSN
2019 Impact Factor: 9.346
2015 SCImago Journal Rankings: 4.974
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorWang, HX-
dc.contributor.authorWan, Q-
dc.contributor.authorLow, KH-
dc.contributor.authorZhou, CY-
dc.contributor.authorHuang, JS-
dc.contributor.authorZhang, JL-
dc.contributor.authorChe, CM-
dc.date.accessioned2020-06-05T06:22:47Z-
dc.date.available2020-06-05T06:22:47Z-
dc.date.issued2020-
dc.identifier.citationChemical Science, 2020, v. 11 n. 8, p. 2243-2259-
dc.identifier.issn2041-6520-
dc.identifier.urihttp://hdl.handle.net/10722/282891-
dc.description.abstractAlkyl-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.languageeng-
dc.publisherRoyal Society of Chemistry: Open Access. The Journal's web site is located at http://www.rsc.org/publishing/journals/sc/About.asp-
dc.relation.ispartofChemical Science-
dc.rightsThis work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.-
dc.subjectCatalyst activity-
dc.subjectChemical stability-
dc.subjectElectronic structure-
dc.subjectIron compounds-
dc.subjectMetal ions-
dc.titleStable group 8 metal porphyrin mono- and bis(dialkylcarbene) complexes: synthesis, characterization, and catalytic activity-
dc.typeArticle-
dc.identifier.emailWang, HX: wanghx1@hku.hk-
dc.identifier.emailWan, Q: wendyqyw@hku.hk-
dc.identifier.emailLow, KH: khlow@hku.hk-
dc.identifier.emailZhou, CY: cyzhou@hku.hk-
dc.identifier.emailHuang, JS: jshuang@hku.hk-
dc.identifier.emailChe, CM: chemhead@hku.hk-
dc.identifier.authorityZhou, CY=rp00843-
dc.identifier.authorityHuang, JS=rp00709-
dc.identifier.authorityChe, CM=rp00670-
dc.description.naturepublished_or_final_version-
dc.identifier.doi10.1039/C9SC05432D-
dc.identifier.scopuseid_2-s2.0-85080856923-
dc.identifier.hkuros310318-
dc.identifier.volume11-
dc.identifier.issue8-
dc.identifier.spage2243-
dc.identifier.epage2259-
dc.identifier.isiWOS:000518011700023-
dc.publisher.placeUnited Kingdom-
dc.identifier.issnl2041-6520-

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