Synthesis, characterization, DFT studies and catalytic activities of manganese(II) complex with 1,4-bis(2,2 ':6,2 ''-terpyridin-4 '-yl) benzene
Mohammad Mahdi Najafpour, Warwick Hillier, Amir Nasser Shamkhali, Mojtaba Amini, Katrin Beckmann, Zvonko Jaglicic, Marko Jagodic, Peter Strauch, Atefeh Nemati Moghaddam, Giangiacomo Beretta, Mojtaba Bagherzadeh
- A new di-manganese complex with "back-to-back" 1,4-bis(2,2':6,2 ''-terpyridin-4'-yl) benzene ligation has been synthesized and characterised by a variety of techniques. The back-to-back ligation presents a novel new mononuclear manganese catalytic centre that functions as a heterogeneous catalysis for the evolution of oxygen in the presence of an exogenous oxidant. We discuss the synthesis and spectroscopic characterizations of this complex and propose a mechanism for oxygen evolution activity of the compound in the presence of oxone. The di-manganese complex also shows efficient and selective catalytic oxidation of sulfides in the presence of H2O2. Density functional theory calculations were used to assess the structural optimization of the complex and a proposed reaction pathway with oxone. The calculations show that middle benzene ring is distorted respect to both of metallic centers, and this in turn leads to negligible resonance of electrons between two sides of complex. The calculations also indicate the unpaired electronA new di-manganese complex with "back-to-back" 1,4-bis(2,2':6,2 ''-terpyridin-4'-yl) benzene ligation has been synthesized and characterised by a variety of techniques. The back-to-back ligation presents a novel new mononuclear manganese catalytic centre that functions as a heterogeneous catalysis for the evolution of oxygen in the presence of an exogenous oxidant. We discuss the synthesis and spectroscopic characterizations of this complex and propose a mechanism for oxygen evolution activity of the compound in the presence of oxone. The di-manganese complex also shows efficient and selective catalytic oxidation of sulfides in the presence of H2O2. Density functional theory calculations were used to assess the structural optimization of the complex and a proposed reaction pathway with oxone. The calculations show that middle benzene ring is distorted respect to both of metallic centers, and this in turn leads to negligible resonance of electrons between two sides of complex. The calculations also indicate the unpaired electron located on oxyl-ligand emphasizes the radical mechanism of water oxidation for the system.…
MetadatenAuthor details: | Mohammad Mahdi Najafpour, Warwick Hillier, Amir Nasser Shamkhali, Mojtaba Amini, Katrin Beckmann, Zvonko Jaglicic, Marko Jagodic, Peter StrauchGND, Atefeh Nemati Moghaddam, Giangiacomo Beretta, Mojtaba Bagherzadeh |
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DOI: | https://doi.org/10.1039/c2dt31544k |
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ISSN: | 1477-9226 |
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Title of parent work (English): | Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry |
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Publisher: | Royal Society of Chemistry |
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Place of publishing: | Cambridge |
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Publication type: | Article |
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Language: | English |
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Year of first publication: | 2012 |
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Publication year: | 2012 |
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Release date: | 2017/03/26 |
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Volume: | 41 |
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Issue: | 39 |
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Number of pages: | 7 |
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First page: | 12282 |
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Last Page: | 12288 |
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Funding institution: | Institute for Advanced Studies in Basic Sciences |
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Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
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Peer review: | Referiert |
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