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Scale of relative Lewis acidities of methyltrioxorhenium and its mono- and bisperoxo derivatives from their equilibria with pyridines; a density functional theory study

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Abstract

The Lewis acidity of methyltrioxorhenium (MTO) and its monoperoxo [A: MeReO2(η 2–O2)] and bisperoxo [B.H 2 O: MeReO(η 2–O2)2(H2O)] derivatives toward pyridine and its derivatives has been theoretically investigated. These compounds, presented in MTO/H2O2 system as one of the most versatile and useful systems, are believed to be active catalysts in oxidation processes. The excellent linear relationships were observed between the equilibrium constants (for the reactions MTO + N = MTO.N, A + N = A.N, and B.H 2 O + N = B.N + H2O; N = pyridine and its derivatives) and either the pK a values of the pyridine and its derivatives or the Hammett σ constants of the substituents on the pyridine. The slope of the plot of log K eq versus pyridines’ pK a and the Hammett ρ values suggests the acidity order as MTO < A < B.H 2 O.

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Acknowledgments

Financial support of the Shiraz Branch, Islamic Azad University is gratefully acknowledged.

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  1. Department of Chemistry, Shiraz Branch, Islamic Azad University, 71993-37635, Shiraz, Iran

    Vahideh Sedaghatzadeh & Fatemeh Niroomand Hosseini

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  1. Vahideh Sedaghatzadeh
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  2. Fatemeh Niroomand Hosseini
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Correspondence to Fatemeh Niroomand Hosseini.

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Sedaghatzadeh, V., Hosseini, F.N. Scale of relative Lewis acidities of methyltrioxorhenium and its mono- and bisperoxo derivatives from their equilibria with pyridines; a density functional theory study. Struct Chem 26, 35–45 (2015). https://doi.org/10.1007/s11224-014-0462-y

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