Competition of methyltrioxorhenium (MTO) with osmium tetroxide (OsO4) for pyridines binding: Ligand binding assay |
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Authors: | Fatemeh Niroomand Hosseini Katayoon KamaliS Masoud Nabavizadeh |
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Institution: | a Department of Chemistry, Islamic Azad University, Shiraz Branch, Shiraz 71993-37635, Iran b Department of Chemistry, College of Sciences, Shiraz University, 71454 Shiraz, Iran |
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Abstract: | Competition of methyltrioxorhenium (MTO) with osmium tetroxide (OsO4) toward L = pyridine and its derivatives, based on the equilibrium constant for the reaction OsO4·L + MTO = MTO·L + OsO4, has been measured. A successful correlation of log Keq with the Hammett σ constants of the substituents on the ligands was realized. A negative reaction constant, obtained for the reactions, shows that a more positive charge expands on the pyridine nitrogen in the complex MTO·L as compared with the complex OsO4·L. So, the rhenium center acts as a better electron acceptor than osmium center. The thermodynamic parameters have been obtained and an excellent linear relationship was observed between the enthalpy and entropy of the reactions. |
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Keywords: | Rhenium Osmium Equilibrium Pyridines |
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