A Combined Mössbauer, Magnetic Circular Dichroism, and Density Functional Theory Approach for Iron Cross-Coupling Catalysis: Electronic Structure, In Situ Formation, and Reactivity of Iron-Mesityl-Bisphosphines
While iron-bisphosphines have emerged as effective catalysts for C—C cross-coupling, the nature of the in situ formed iron species, elucidation of the active catalysts and the mechanisms of catalysis have remained elusive. A combination of Fe Mössbauer and magnetic circular dichroism (MCD) spectrosc...
| Publicado en: | Journal of the American Chemical Society Vol. 136; no. 25; pp. 9132 - 9144 |
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| Autores principales: | , , , , |
| Formato: | Artículo |
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American Chemical Society
6/25/2014
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=96970719&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 96970719 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 6/25/2014 vid: 136 iid: 25 pid: 997 pub: American Chemical Society artinfo: ui: 96970719 10.1021/ja503596m ppf: 9132 ppct: 12 formats: tig: atl: A Combined Mössbauer, Magnetic Circular Dichroism, and Density Functional Theory Approach for Iron Cross-Coupling Catalysis: Electronic Structure, In Situ Formation, and Reactivity of Iron-Mesityl-Bisphosphines aug: au: Daifuku, Stephanie L. Al-Afyouni, Malik H. Snyder, Benjamin E. R. Kneebone, Jared L. Neidig, Michael L. affil: Department of Chemistry, University of Rochester, Rochester, New York 14627, United States su: Iron compounds Diphosphine Mössbauer spectroscopy Magnetic circular dichroism Density functional theory Coupling reactions (Chemistry) Electronic structure Reaction mechanisms (Chemistry) sug: subj: Iron compounds Diphosphine Mössbauer spectroscopy Magnetic circular dichroism Density functional theory Coupling reactions (Chemistry) Electronic structure Reaction mechanisms (Chemistry) ab: While iron-bisphosphines have emerged as effective catalysts for C—C cross-coupling, the nature of the in situ formed iron species, elucidation of the active catalysts and the mechanisms of catalysis have remained elusive. A combination of Fe Mössbauer and magnetic circular dichroism (MCD) spectroscopies of well-defined and in situ formed mesityl-iron(II)-SciOPP species combined with density functional theory (DFT) investigations provides the first direct insight into electronic structure, bonding and in situ speciation of mesityl-iron(Il)-bisphosphines in the Kumada cross-coupling of MesMgBr and primary alkyl halides using FeCl(SciOPP). Combined with freeze-trapped solution Mossbauer studies of reactions with primary alkyl halides, these studies demonstrate that distorted square-planar FeMes(SciOPP) is the active catalyst for cross-coupling and provide insight into the molecular-level mechanism of catalysis. These studies also define the effects of key reaction protocol details, including the role of the slow Grignard addition method and the addition of excess SciOPP ligand, in leading to high product yields and selectivities. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2014 holdings: @attributes: islocal: N |
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