Mono‐ and Dinuclear Heteroleptic Cobalt Complexes with α‐Diimine and Polyarene Ligands |
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| Authors: | Xuting Wang Dr. Yanxia Zhao Shida Gong Prof. Bin Liu Prof. Qian‐Shu Li Prof. Ji‐Hu Su Prof. Biao Wu Prof. Xiao‐Juan Yang |
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| Affiliation: | 1. Key Laboratory of Synthetic and Natural Functional Molecular, Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710069 (P.R. China);2. Center for Computational Quantum Chemistry, South China Normal University, Guangzhou 510631 (P.R. China);3. Hefei National Laboratory for Physical Sciences at Microscale and Department of Modern Physics, University of Science and Technology of China, Hefei 230026 (P.R. China) |
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| Abstract: | Reactions of the dimeric cobalt complex [(L?Co)2] ( 1 , L=[(2,6‐iPr2C6H3)NC(Me)]2) with polyarenes afforded a series of mononuclear and dinuclear complexes: [LCo(η4‐anthracene)] ( 2 ), [LCo(μ‐η4:η4‐naphthalene)CoL] ( 3 ), and [LCo(μ‐η4:η4‐phenanthrene)CoL] ( 4 ). The pyrene complexes [{Na2(Et2O)2}{LCo(μ‐η3:η3‐pyrene)CoL}] ( 5 ) and [{Na2(Et2O)3}{LCo(η3‐pyrene)}] ( 6 ) were obtained by treating precursor 1 with pyrene followed by reduction with Na metal. These complexes contain three potential redox active centers: the cobalt metal and both α‐diimine and polyarene ligands. Through a combination of X‐ray crystallography, EPR spectroscopy, magnetic susceptibility measurement, and DFT computations, the electronic configurations of these complexes were studied. It was determined that complexes 2 – 4 have a high‐spin CoI center coupled with a radical α‐diimine ligand and a neutral polyarene ligand. Whereas, the ligand L in complexes 5 and 6 has been further reduced to the dianion, the cobalt remains in a formal (I) oxidation state, and the pyrene molecule is either neutral or monoanionic. |
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| Keywords: | alpha‐diimine cobalt electronic structure non‐innocent ligands polyarene |
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