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Title: Anisole as an ambidentate ligand: Ab initio molecular orbital study of alkali metal cations binding to anisole

Abstract

The authors present optimized geometries and binding energies for alkali metal cation complexes with anisole (methoxybenzene). Results are obtained for Li{sup +} through Cs{sup +} at the RHF/6-311G* and MP2/6-311+G* levels of theory, with K{sup +}, Rb{sup +}, and Cs{sup +} represented by relativistic ECPs and associated valence basis sets. RHF/6-311G{sup {minus}} frequencies are used to verify that the optimized geometries are minima and to calculate binding enthalpies. The effects of basis set superposition error (BSSE) are estimated at both the RHF and MP2 levels. The alkali metals bind to anisole in two ways, either predominantly through interactions with the aromatic ring or with the ether oxygen. For binding to the ring, BSSE-corrected MP2/6-311+G* binding enthalpies (in kcal/mol) of {minus}38.1 (Li{sup +}), {minus}23.6 (Na{sup +}), {minus}18.3 (K{sup +}), {minus}15.4 (Rb{sup +}), and {minus}13.6 (Cs{sup +}) were obtained. The average distances (in {angstrom}) between the ring carbons and the cations are 2.33 (Li{sup +}), 2.79 (Na{sup +}), 3.20 (K{sup +}), 3.44 (Rb{sup +}), and 3.70 (Cs{sup +}). For binding to the ether oxygen, the BSSE-corrected MP2/6-311+G* binding enthalpies (in kcal/mol) are {minus}37.6 (Li{sup +}), {minus}25.2 (Na{sup +}), {minus}19.4 (K{sup +}), {minus}16.4 (Rb{sup +}), and {minus}14.3 (Cs{sup +}). The distances (in {angstrom})more » between the ether oxygen and the cations are 1.82 (Li{sup +}), 2.24 (Na{sup +}), 2.62 (K{sup +}), 2.87 (Rb{sup +}), and 3.10 (Cs{sup +}). Although the differences in binding energy between the two sites are small, the cations generally prefer to bind to the oxygen.« less

Authors:
;
Publication Date:
Research Org.:
Pacific Northwest National Lab., Richland, WA (US)
OSTI Identifier:
20013060
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
Additional Journal Information:
Journal Volume: 103; Journal Issue: 48; Other Information: PBD: 2 Dec 1999; Journal ID: ISSN 1089-5639
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; ANISOLE; LIGANDS; MOLECULAR ORBITAL METHOD; ALKALI METALS; ENTHALPY; CATIONS

Citation Formats

Nicholas, J B, and Hay, B P. Anisole as an ambidentate ligand: Ab initio molecular orbital study of alkali metal cations binding to anisole. United States: N. p., 1999. Web. doi:10.1021/jp990570p.
Nicholas, J B, & Hay, B P. Anisole as an ambidentate ligand: Ab initio molecular orbital study of alkali metal cations binding to anisole. United States. https://doi.org/10.1021/jp990570p
Nicholas, J B, and Hay, B P. 1999. "Anisole as an ambidentate ligand: Ab initio molecular orbital study of alkali metal cations binding to anisole". United States. https://doi.org/10.1021/jp990570p.
@article{osti_20013060,
title = {Anisole as an ambidentate ligand: Ab initio molecular orbital study of alkali metal cations binding to anisole},
author = {Nicholas, J B and Hay, B P},
abstractNote = {The authors present optimized geometries and binding energies for alkali metal cation complexes with anisole (methoxybenzene). Results are obtained for Li{sup +} through Cs{sup +} at the RHF/6-311G* and MP2/6-311+G* levels of theory, with K{sup +}, Rb{sup +}, and Cs{sup +} represented by relativistic ECPs and associated valence basis sets. RHF/6-311G{sup {minus}} frequencies are used to verify that the optimized geometries are minima and to calculate binding enthalpies. The effects of basis set superposition error (BSSE) are estimated at both the RHF and MP2 levels. The alkali metals bind to anisole in two ways, either predominantly through interactions with the aromatic ring or with the ether oxygen. For binding to the ring, BSSE-corrected MP2/6-311+G* binding enthalpies (in kcal/mol) of {minus}38.1 (Li{sup +}), {minus}23.6 (Na{sup +}), {minus}18.3 (K{sup +}), {minus}15.4 (Rb{sup +}), and {minus}13.6 (Cs{sup +}) were obtained. The average distances (in {angstrom}) between the ring carbons and the cations are 2.33 (Li{sup +}), 2.79 (Na{sup +}), 3.20 (K{sup +}), 3.44 (Rb{sup +}), and 3.70 (Cs{sup +}). For binding to the ether oxygen, the BSSE-corrected MP2/6-311+G* binding enthalpies (in kcal/mol) are {minus}37.6 (Li{sup +}), {minus}25.2 (Na{sup +}), {minus}19.4 (K{sup +}), {minus}16.4 (Rb{sup +}), and {minus}14.3 (Cs{sup +}). The distances (in {angstrom}) between the ether oxygen and the cations are 1.82 (Li{sup +}), 2.24 (Na{sup +}), 2.62 (K{sup +}), 2.87 (Rb{sup +}), and 3.10 (Cs{sup +}). Although the differences in binding energy between the two sites are small, the cations generally prefer to bind to the oxygen.},
doi = {10.1021/jp990570p},
url = {https://www.osti.gov/biblio/20013060}, journal = {Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory},
issn = {1089-5639},
number = 48,
volume = 103,
place = {United States},
year = {Thu Dec 02 00:00:00 EST 1999},
month = {Thu Dec 02 00:00:00 EST 1999}
}