THE COORDINATION CHEMISTRY OF FLUOROCARBONS - GROUP-I AND GROUP-II METAL-ION COMPLEXES OF FLUORO MACROCYCLES

Citation
H. Plenio et R. Diodone, THE COORDINATION CHEMISTRY OF FLUOROCARBONS - GROUP-I AND GROUP-II METAL-ION COMPLEXES OF FLUORO MACROCYCLES, Chemische Berichte, 130(7), 1997, pp. 963-968
Citations number
16
Categorie Soggetti
Chemistry
Journal title
ISSN journal
00092940
Volume
130
Issue
7
Year of publication
1997
Pages
963 - 968
Database
ISI
SICI code
0009-2940(1997)130:7<963:TCCOF->2.0.ZU;2-U
Abstract
Two new fluoro macrocycles BenzoFN(2)O(3) and F(N2O2)(2)C2H4 were synt hesized in the reactions of 1,3-bis(bromomethyl)-2fluorobenzene with b enzo-diaza-15-crown-5 and 1,2-bis(diaza-12-crown-4)ethane, respectivel y, in 30% yield each. Close CF...metal ion interactions in the respect ive alkaline metal complexes in solution are evidenced by characterist ic shifts of the F-19-NMR resonances of up to delta = 18.7 relative to the free ligand and by a decrease of the (1)J(CF) coupling constant o f up to 20 Hz, which is most pronounced in BenzoFN(2)O(3) . Li+ and F( N2O2)(2)C2H4 . K+. In BenzoFN(2)O(3) . Li+ a (1)J(F-19-Li-7) of 15.5 H z was observed, which is indicative of very close CF...Li+ interaction s in solution. In the X-ray crystal structures of BenzoFN(2)O(3) . Na [CF...Na+ 246.8(2) pm], 26-fluoro-4,7,13, 16-tetraoxa-1, 10-diazatric yclo[8.8.7.1(20,24)]-hexacosa-20,22,24 (26)triene . Na+ {CF...Na+ 267. 1(2) pm} and ,9,12,15,18-hexaoxabicyclo[18.3.1(1,20)]henei-cosa -1(24) ,20,22-triene . Ba2+ [CF...Ba2+ 299.0(3) pm] short CF...metal interact ions were found. Such close CF...metal ion interactions do not result in a lengthening of the C-F bonds, which is not a sign of weak CF...me tal ion interactions, since a Cambridge Structural Database search rev ealed that a shortening of the C-O bond length is also not observed in crown ether complexes of alkaline metals.