دورية أكاديمية
Cp*Co(III) catalysts with proton-responsive ligands for carbon dioxide hydrogenation in aqueous media.
| العنوان: | Cp*Co(III) catalysts with proton-responsive ligands for carbon dioxide hydrogenation in aqueous media. |
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| المؤلفون: | Badiei YM; Chemistry Department, Brookhaven National Laboratory , Upton, New York 11973, United States., Wang WH, Hull JF, Szalda DJ, Muckerman JT, Himeda Y, Fujita E |
| المصدر: | Inorganic chemistry [Inorg Chem] 2013 Nov 04; Vol. 52 (21), pp. 12576-86. Date of Electronic Publication: 2013 Oct 16. |
| نوع المنشور: | Journal Article; Research Support, Non-U.S. Gov't; Research Support, U.S. Gov't, Non-P.H.S. |
| اللغة: | English |
| بيانات الدورية: | Publisher: American Chemical Society Country of Publication: United States NLM ID: 0366543 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1520-510X (Electronic) Linking ISSN: 00201669 NLM ISO Abbreviation: Inorg Chem Subsets: MEDLINE |
| أسماء مطبوعة: | Original Publication: [Easton, Pa.] American Chemical Society. |
| مواضيع طبية MeSH: | Carbon Dioxide/*chemistry , Cobalt/*chemistry , Organometallic Compounds/*chemistry, Catalysis ; Chemistry Techniques, Synthetic ; Crystallography, X-Ray ; Formates ; Hydrogenation ; Ligands ; Magnetic Resonance Spectroscopy ; Molecular Structure ; Organometallic Compounds/chemical synthesis ; Protons ; Solutions ; Water/chemistry |
| مستخلص: | New water-soluble pentamethylcyclopentadienyl cobalt(III) complexes with proton-responsive 4,4'- and 6,6'-dihydroxy-2,2'-bipyridine (4DHBP and 6DHBP, respectively) ligands have been prepared and were characterized by X-ray crystallography, UV-vis and NMR spectroscopy, and mass spectrometry. These cobalt(III) complexes with proton-responsive ligands predominantly exist in their deprotonated [Cp*Co(DHBP-2H(+))(OH2)] forms with stronger electron-donating properties in neutral and basic solutions, and are active catalysts for CO2 hydrogenation in aqueous bicarbonate media at moderate temperature under a total 4-5 MPa (CO2:H2 1:1) pressure. The cobalt complexes containing 4DHBP ligands ([1-OH2](2+) and [1-Cl](+), where 1 = Cp*Co(4DHBP)) display better thermal stability and exhibit notable catalytic activity for CO2 hydrogenation to formate in contrast to the catalytically inactive nonsubstituted bpy analogues [3-OH2](2+) (3 = Cp*Co(bpy)). While the catalyst Cp*Ir(6DHBP)(OH2)(2+) in which the pendent oxyanion lowers the barrier for H2 heterolysis via proton transfer through a hydrogen-bonding network involving a water molecule is remarkably effective (ACS Catal. 2013, 3, 856-860), cobalt complexes containing 6DHBP ligands ([2-OH2](2+) and [2-Cl](+), 2 = Cp*Co(6DHBP)) exhibit lower TOF and TON for CO2 hydrogenation than those with 4DHBP. The low activity is attributed to thermal instability during the hydrogenation of CO2 as corroborated by DFT calculations. |
| المشرفين على المادة: | 0 (Formates) 0 (Ligands) 0 (Organometallic Compounds) 0 (Protons) 0 (Solutions) 059QF0KO0R (Water) 0YIW783RG1 (formic acid) 142M471B3J (Carbon Dioxide) 3G0H8C9362 (Cobalt) |
| تواريخ الأحداث: | Date Created: 20131018 Date Completed: 20140822 Latest Revision: 20161125 |
| رمز التحديث: | 20231215 |
| DOI: | 10.1021/ic401707u |
| PMID: | 24131038 |
| قاعدة البيانات: | MEDLINE |
Find this issue from the American Chemical Society | تدمد: | 1520-510X |
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| DOI: | 10.1021/ic401707u |