Mössbauer Spectroscopy and Theoretical Studies of Iron Bimetallic Complexes Showing Electrocatalytic Hydrogen Evolution
| Autor: | Pokhraj Ghosh, Michael B. Hall, Morgan Cohara, Codrina V. Popescu, Shengda Ding |
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| Rok vydání: | 2019 |
| Předmět: |
010405 organic chemistry
Ligand Chemistry 010402 general chemistry 01 natural sciences 0104 chemical sciences Inorganic Chemistry Crystallography Cyclopentadienyl complex Mössbauer spectroscopy Diamagnetism Density functional theory Physical and Theoretical Chemistry Ground state Hyperfine structure Bimetallic strip |
| Zdroj: | Inorganic Chemistry. 58:7069-7077 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/acs.inorgchem.9b00746 |
| Popis: | Mossbauer spectroscopy and density functional theory (DFT) calculations are reported for the mononuclear Fe–nitrosyl complex [Fe(N,N′-bis(2-mercaptoethyl)-1,4-diazacycloheptane)NO] {[Fe(bme-dach)(NO)] (1)} and the series of dithiolate-bridged dinuclear complexes M-Fe(CO)Cp [M = Fe(bme-dach)(NO) (1-A), Ni(bme-dach) (2-A), and Co(bme-dach)(NO) (3-A)], in which M is a metallo-ligand to Fe(CO)Cp+ (Fe′Cp). The latter is an organometallic fragment in which Fe is coordinated by one CO and one cyclopentadienyl ligand. Complexes 1-A and 2-A were previously shown to have electrocatalytic hydrogen evolution activity. Mononuclear {Fe-NO}7 complex 1, with overall spin of 1/2, has an isomer shift of 0.23(2) mm/s [ΔEQ = 1.37(2) mm/s] and magnetic hyperfine couplings of {−38 T, −26.8 T, 8.6 T}. In complexes 2-A and 3-A, Fe′(CO)Cp+ has a diamagnetic ground state and δ = 0.33(2) mm/s (ΔEQ ≈ 1.78 mm/s), consistent with a low-spin FeII site. In contrast, in complex 1-A, M = Fe(bme-dach)(NO) (i.e., complex 1) the magnetic hyp... |
| Databáze: | OpenAIRE |
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