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A theoretical view on the thermodynamic cistrans equilibrium of dihalo ruthenium olefin metathesis (pre-)catalysts

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Abstract

This work was conducted to provide an overview on the position of the thermodynamic cistrans equilibrium of 85 conventional and X-chelated alkylidene-ruthenium complexes (X=O, S, Se, N, P, Cl, I, Br). The reported energies (ΔE) were obtained through single-point calculations with M06 functional and TZVP basis set from BP86/SVP-optimized cis- and trans-dichloro geometries and using the polarizable continuum model to simulate the influence of the solvent. Dichloromethane and toluene were selected as examples for solvents with high and low dielectric constants. The obtained relative stabilities of the cis- and trans-dihalo derivatives of the respective alkylidene complexes will serve for a better explanation of their catalytic activity as has been disclosed herein with selected examples.

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Acknowledgments

E. P. gratefully acknowledges to “Chemical Monthly” for financial support of this work.

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Correspondence to Eva Pump.

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Pump, E., Cavallo, L. & Slugovc, C. A theoretical view on the thermodynamic cistrans equilibrium of dihalo ruthenium olefin metathesis (pre-)catalysts. Monatsh Chem 146, 1131–1141 (2015). https://doi.org/10.1007/s00706-015-1433-8

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  • DOI: https://doi.org/10.1007/s00706-015-1433-8

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