Panda, Chakadola and Debgupta, Joyashish and Diaz, David Diaz and Singh, Kundan K. and Gupta, Sayam Sen and Dhar, Basab B. (2014) Homogeneous Photochemical Water Oxidation by Biuret-Modified Fe-TAML: Evidence of Fe-V(O) Intermediate. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 136 (35). pp. 12273-12282. ISSN 0002-7863,
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Water splitting, leading to hydrogen and oxygen in a process that mimics natural photosynthesis, is extremely important for devising a sustainable solar energy conversion system. Development of earth-abundant, transition metal-based catalysts that mimic the oxygen-evolving complex of photosystem II, which is involved in oxidation of water to O-2 during natural photosynthesis, represents a major challenge. Further, understanding the exact mechanism, including elucidation of the role of active metal-oxo intermediates during water oxidation (WO), is critical to the development of more efficient catalysts. Herein, we report Fe-III complexes of biuret-modified tetra-amidomacrocyclic ligands (Fe-TAML; 1a and 1b) that catalyze fast, homogeneous, photochemical WO to give OD with moderate efficiency (maximum TON = 220, TOF = 0.76 s(-1)). Previous studies on photochemical WO using iron complexes resulted in demetalation of the iron complexes with concomitant formation of iron oxide nanoparticles (NPs) that were responsible for WO. Herein, we show for the first time that a high valent Fe-V(O) intermediate species is photochemically generated as the active intermediate for the oxidation of water to O2. To the best of our knowledge, this represents the first example of a molecular iron complex catalyzing photochemical WO through a Fe-V(O) intermediate.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | MOLECULAR RUTHENIUM CATALYST; PHOTOSYSTEM-II; IRON COMPLEXES; MACROCYCLIC LIGAND; HYDROGEN-PEROXIDE; AQUEOUS-SOLUTION; BOND FORMATION; IRIDIUM; OXYGEN; EFFICIENT; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie > Arbeitskreis Prof. Dr. David Díaz Díaz |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 14 Aug 2019 09:35 |
| Last Modified: | 14 Aug 2019 09:35 |
| URI: | https://pred.uni-regensburg.de/id/eprint/9569 |
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