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Title: Cation-ether complexes in the gas phase: Bond dissociation energies of Na{sup +}(dimethyl ether){sub x}, x = 1-4; Na{sup +}(1,2-dimethoxyethane){sub x}, x = 1 and 2; and Na{sup +}(12-crown-4)

Abstract

Bond dissociation energies of Na{sup +}[O(CH{sub 3}){sub 2}]{sub x}, x = 1-4; Na{sup +}[(CH{sub 2}OCH{sub 3}){sub 2}]{sub x}, x = 1 and 2; and Na{sup +}[c-(C{sub 2}H{sub 4}O){sub 4}] are reported. The bond dissociation energies are determined experimentally by analysis of the thresholds for collision-induced dissociation of the cation-ether complexes by xenon measured using guided ion beam mass spectrometry. In all cases, the primary and lowest energy dissociation channel observed experimentally is endothermic loss of one ligand molecule. The cross section thresholds are interpreted to yield 0 and 298 K bond dissociation energies after accounting for the effects of multiple ion-molecule collisions, internal energy of the complexes, and unimolecular decay rates. Trends in the bond dissociation energies determined by experiment and recent theoretical ab initio calculations are in good agreement. Our best experimental values, which have an average uncertainty of {+-}7 kJ/mol, are lower than the theoretical values by 7 {+-} 5 kJ/mol per metal-oxygen interaction. These values are compared with bond dissociation energies for the comparable lithium cation-ether complexes. This comparison reveals the thermodynamic consequences of ligand-ligand repulsion. 51 refs., 5 figs., 4 tabs.

Authors:
;  [1];  [2]
  1. Univ. of Utah, Salt Lake City, UT (United States)
  2. Pacific Northwest National Lab., Richland, WA (United States)
Publication Date:
OSTI Identifier:
501894
DOE Contract Number:  
AC06-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory; Journal Volume: 101; Journal Issue: 5; Other Information: PBD: 30 Jan 1997
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; 99 MATHEMATICS, COMPUTERS, INFORMATION SCIENCE, MANAGEMENT, LAW, MISCELLANEOUS; 66 PHYSICS; SODIUM COMPLEXES; DISSOCIATION; DISSOCIATION ENERGY; ETHERS; EXPERIMENTAL DATA; ION-MOLECULE COLLISIONS; MASS SPECTRA; CALCULATION METHODS

Citation Formats

More, M.B., Armentrout, P.B., and Ray, D. Cation-ether complexes in the gas phase: Bond dissociation energies of Na{sup +}(dimethyl ether){sub x}, x = 1-4; Na{sup +}(1,2-dimethoxyethane){sub x}, x = 1 and 2; and Na{sup +}(12-crown-4). United States: N. p., 1997. Web. doi:10.1021/jp962851s.
More, M.B., Armentrout, P.B., & Ray, D. Cation-ether complexes in the gas phase: Bond dissociation energies of Na{sup +}(dimethyl ether){sub x}, x = 1-4; Na{sup +}(1,2-dimethoxyethane){sub x}, x = 1 and 2; and Na{sup +}(12-crown-4). United States. doi:10.1021/jp962851s.
More, M.B., Armentrout, P.B., and Ray, D. Thu . "Cation-ether complexes in the gas phase: Bond dissociation energies of Na{sup +}(dimethyl ether){sub x}, x = 1-4; Na{sup +}(1,2-dimethoxyethane){sub x}, x = 1 and 2; and Na{sup +}(12-crown-4)". United States. doi:10.1021/jp962851s.
@article{osti_501894,
title = {Cation-ether complexes in the gas phase: Bond dissociation energies of Na{sup +}(dimethyl ether){sub x}, x = 1-4; Na{sup +}(1,2-dimethoxyethane){sub x}, x = 1 and 2; and Na{sup +}(12-crown-4)},
author = {More, M.B. and Armentrout, P.B. and Ray, D.},
abstractNote = {Bond dissociation energies of Na{sup +}[O(CH{sub 3}){sub 2}]{sub x}, x = 1-4; Na{sup +}[(CH{sub 2}OCH{sub 3}){sub 2}]{sub x}, x = 1 and 2; and Na{sup +}[c-(C{sub 2}H{sub 4}O){sub 4}] are reported. The bond dissociation energies are determined experimentally by analysis of the thresholds for collision-induced dissociation of the cation-ether complexes by xenon measured using guided ion beam mass spectrometry. In all cases, the primary and lowest energy dissociation channel observed experimentally is endothermic loss of one ligand molecule. The cross section thresholds are interpreted to yield 0 and 298 K bond dissociation energies after accounting for the effects of multiple ion-molecule collisions, internal energy of the complexes, and unimolecular decay rates. Trends in the bond dissociation energies determined by experiment and recent theoretical ab initio calculations are in good agreement. Our best experimental values, which have an average uncertainty of {+-}7 kJ/mol, are lower than the theoretical values by 7 {+-} 5 kJ/mol per metal-oxygen interaction. These values are compared with bond dissociation energies for the comparable lithium cation-ether complexes. This comparison reveals the thermodynamic consequences of ligand-ligand repulsion. 51 refs., 5 figs., 4 tabs.},
doi = {10.1021/jp962851s},
journal = {Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory},
number = 5,
volume = 101,
place = {United States},
year = {Thu Jan 30 00:00:00 EST 1997},
month = {Thu Jan 30 00:00:00 EST 1997}
}