NMR-STUDY OF CROWN-ETHER MOTION IN 2 ALKALIDES

被引:12
作者
WAGNER, MJ
MCMILLS, LEH
ELLABOUDY, AS
EGLIN, JL
DYE, JL
EDWARDS, PP
PYPER, NC
机构
[1] MICHIGAN STATE UNIV,DEPT CHEM,E LANSING,MI 48824
[2] MICHIGAN STATE UNIV,CTR FUNDAMENTAL MAT RES,E LANSING,MI 48824
[3] UNIV CAMBRIDGE,CHEM LAB,CAMBRIDGE CB2 1EW,ENGLAND
关键词
D O I
10.1021/j100203a018
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Nuclear spin-lattice relaxation times (T1) of both Cs-133 and Na-23 were measured as a function of temperature for two cesium sodides, Cs+(18-crown-6)2Na- and Cs+(15-crown-5)2Na-. A logarithmic dependence of the T1 values of these two compounds on the inverse temperature is interpreted as the result of crown ether rotational/conformational reorientation with average activation barriers of 31.2 and 35.4 kJ mol-1, respectively. This interpretation is supported by the line-width reduction of the Na-23 resonances, reduction of the observed Na-23 quadrupole coupling constants, and the disappearance of peaks in the powder X-ray diffraction patterns. The line-width data are used with the approximate formula of Waugh (Waugh, J. S.; Fedin, E. 1. Sov. Phys. Solid State 1963, 4, 1633) to yield activation barriers in good agreement with the nuclear spin-lattice relaxation analysis.
引用
收藏
页码:9656 / 9660
页数:5
相关论文
共 31 条
[1]  
ANDREW ER, 1953, P ROY SOC LOND A MAT, V216, P405
[2]  
BOBEL D, 1979, J MAGN RESON, V36, P371
[3]   SOLID-PHASE STEREOCHEMICAL DYNAMICS OF 18-CROWN-6 ETHER AND ITS KNCS COMPLEX AS STUDIED BY LOW-TEMPERATURE C-13 NUCLEAR-MAGNETIC-RESONANCE [J].
BUCHANAN, GW ;
KIRBY, RA ;
RIPMEESTER, JA ;
RATCLIFFE, CI .
TETRAHEDRON LETTERS, 1987, 28 (41) :4783-4786
[4]   MACROCYCLE REORIENTATION IN SOLID 18-CROWN-6 COMPLEXES DETECTED BY H-1 AND C-13 NMR-SPECTROSCOPY [J].
BUCHANAN, GW ;
MORAT, C ;
RATCLIFFE, CI ;
RIPMEESTER, JA .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1989, (18) :1306-1308
[5]  
Chihara H., 1980, ADV NUCL QUADRUPOLE, V4
[6]   QUADRUPOLE EFFECTS IN NUCLEAR MAGNETIC RESONANCE STUDIES OF SOLIDS [J].
COHEN, MH ;
REIF, F .
SOLID STATE PHYSICS, 1957, 5 :321-438
[8]   CRYSTAL-STRUCTURES AND PROPERTIES OF 2 SODIDES AND AN ELECTRIDE [J].
DAWES, SB ;
WARD, DL ;
FUSSARYDEL, O ;
HUANG, RH ;
DYE, JL .
INORGANIC CHEMISTRY, 1989, 28 (11) :2132-2136
[9]   CESIUM-133 SOLID-STATE NUCLEAR-MAGNETIC-RESONANCE SPECTROSCOPY OF ALKALIDES AND ELECTRIDES [J].
DAWES, SB ;
ELLABOUDY, AS ;
DYE, JL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (12) :3508-3513
[10]   X-RAY-POWDER DIFFRACTION STUDIES OF ALKALIDES AND ELECTRIDES THAT CONTAIN 15-CROWN-5 [J].
DOEUFF, S ;
TSAI, KL ;
DYE, JL .
INORGANIC CHEMISTRY, 1991, 30 (04) :849-851