Iron Complexes Bearing Diphosphine Ligands with Positioned Pendant Amines as Electrocatalysts for the Oxidation of H2
| Autor: | Daniel L. DuBois, R. Morris Bullock, Elliott B. Hulley, Tianbiao Liu, Molly O'Hagan, Qian Liao |
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| Rok vydání: | 2015 |
| Předmět: |
chemistry.chemical_classification
Hydrogen Base (chemistry) Chemistry Organic Chemistry Inorganic chemistry Substituent chemistry.chemical_element Electrochemistry Medicinal chemistry Single Crystal Diffraction Catalysis Inorganic Chemistry chemistry.chemical_compound Catalytic oxidation Amine gas treating Physical and Theoretical Chemistry |
| Zdroj: | Organometallics. 34:2747-2764 |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/om501289f |
| Popis: | The synthesis and spectroscopic characterization of CpC5F4NFe(PtBu2NBn2)Cl, [3-Cl] (where C5F4N is a tetrafluoropyridyl substituent and PtBu2NBn2 = 1,5-dibenzyl-3,7-di(tert-butyl)-1,5-diaza-3,7-diphosphacyclooctane), are reported. Complex 3-Cl and [CpC5F4NFe(PtBu2NtBu2)Cl], 4-Cl, are precursors to intermediates in the catalytic oxidation of H2, including CpC5F4NFe(PtBu2NBn2)H (3-H), CpC5F4NFe(PtBu2NtBu2)H (4-H), [CpC5F4NFe(PtBu2NBn2)]BArF4 ([3](BArF4), [CpC5F4NFe(PtBu2NtBu2)]BArF4 ([4](BArF4), [CpC5F4NFe(PtBu2NBn2)(H2)]BArF4 ([3-H2]BArF4), and [CpC5F4NFe(PtBu2NtBu2H)H]BArF4 ([4-FeH(NH)]BArF4). All of these complexes were characterized by spectroscopic and electrochemical studies; 3-Cl, 3-H, and 4-Cl were also characterized by single crystal diffraction studies. 3-H and 4-H are electrocatalysts for H2 (1.0 atm) oxidation in the presence of an excess of the amine bases N-methylpyrrolidine, Et3N or iPr2EtN. Turnover frequencies at 22 °C for 3-H and 4-H with N-methylpyrrolidine as the base are 2.5 and 0.5 s–1... |
| Databáze: | OpenAIRE |
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