caa a22 4500 445328460 CHVBK 20180317142729.0 cr unu---uuuuu 170323e20110901xx s 000 0 eng 10.1007/s10953-011-9732-0 doi (NATIONALLICENCE)springer-10.1007/s10953-011-9732-0 Solvation of Metal Cations in Non-aqueous Liquids [Elektronische Daten] [Michael Ziegler, Jeffry Madura] The role that alkali cations in non-aqueous solvents play in organic reactions continues to be a topic of interest. In particular it has been observed that these cations can alter the stereoselectivity of organic reactions. Our interest is to first understand the nature of cation-ether complexes, then to investigate the role that the cation plays in the reaction. We have used the electronic structure techniques Hartree-Fock (HF), Second-order Møller-Plesset perturbation theory (MP2), and the Becke three-parameter exchange functional coupled with the nonlocal correlation functional of Lee, Yang, and Parr (B3LYP) to study the structure and properties of tetrahydrofuran (THF) and dimethyl ether (DME) solvation complexes with Li+, Na+, K+, Cu+, and MgCl+. The values calculated for DME complexes were compared with existing experimentally determined data. The B3LYP/6-31+G∗ model chemistry was found to be the most accurate and efficient method of modeling the cation-DME molecular system. The energetic trends observed in the DME results were also observed in the THF data. Based on the accuracy of the calculations and the computational cost of the calculations, B3LYP was found to be the most desirable method of modeling these types of systems. Springer Science+Business Media, LLC, 2011 Ab initio calculations nationallicence Density functional theory nationallicence Cation-ether complexes nationallicence Explicit solvation nationallicence Continuum solvation approximation nationallicence Ziegler Michael Center for Computational Sciences, Department of Chemistry & Biochemistry, Duquesne University, 600 Forbes Avenue, 15282-1530, Pittsburgh, PA, USA aut Madura Jeffry Center for Computational Sciences, Department of Chemistry & Biochemistry, Duquesne University, 600 Forbes Avenue, 15282-1530, Pittsburgh, PA, USA aut Journal of Solution Chemistry Springer US; http://www.springer-ny.com 40/8(2011-09-01), 1383-1398 0095-9782 40:8<1383 2011 40 10953 https://doi.org/10.1007/s10953-011-9732-0 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s10953-011-9732-0 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Ziegler Michael Center for Computational Sciences, Department of Chemistry & Biochemistry, Duquesne University, 600 Forbes Avenue, 15282-1530, Pittsburgh, PA, USA aut NATIONALLICENCE 700 1- Madura Jeffry Center for Computational Sciences, Department of Chemistry & Biochemistry, Duquesne University, 600 Forbes Avenue, 15282-1530, Pittsburgh, PA, USA aut NATIONALLICENCE 773 0- Journal of Solution Chemistry Springer US; http://www.springer-ny.com 40/8(2011-09-01), 1383-1398 0095-9782 40:8<1383 2011 40 10953 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer