A study of C-F...M(+) interaction: metal complexes of fluorine-containing cage compounds.
The C-F...M(+) interaction was investigated by observation of the NMR spectroscopic changes and complexation studies between metal cations and the cage compounds 1 and 2 which have fluorobenzene units as donor atoms. As a result, the interaction was detected with all of the metal cations which form complexes with 1 and 2. The stability of the complexes of 1 and 2 was determined by the properties of the metal cations (ionic radii and degree of hydrolysis), not by the hard-soft nature of the cations. Crystallographic analyses of Tl(+) subset 1 and La(3+) subset 2 provided structural information (interatomic distances and bond angles), and the bond strengths, C-F...M(+), O...M(+), and N...M(+), were estimated by Brown's equation based on the structural data. Short C-F...Tl(+) (2.952-3.048 A) distances were observed in the complex Tl(+) subset 1. The C-F bond lengths in the complexes, Tl(+) subset 1 and La(3+) subset 2, are elongated compared to those of the metal-free compounds. Interestingly, no solvent molecules including water molecules were coordinated to La(3+) in the La(3+) subset 2. The stabilization energy of cation-dipole interaction was calculated on the basis of the data from X-ray crystallographic analysis, and it is roughly consistent with the (-)Delta H values estimated in solution. Thus, the C-F...M(+) interaction can be expressed by the cation-dipole interaction. This result explains the fact that compound 1 which has fluorine atom as hard donor strongly binds soft metals such as Ag(+) and Tl(+). Furthermore, it was concluded that the fluorobenzene unit has a poor electron-donating ability compared to that of ether oxygen or amine nitrogen, and thus the ratio of the coordination bond in C-F...M(+) is small. The specific and remarkable changes in the (1)H, (13)C, and (19)F NMR spectra were observed accompanied by the complexation between M(+) and the hosts 1 and 2. These spectral features are important tools for the investigation of the C-F...M(+) interaction. Furthermore, F.Tl(+) spin couplings were observed at room temperature in the Tl(+) subset 1, 2 (J(F-Tl) = 2914 Hz for Tl(+) subset 1 and 4558 Hz for Tl(+) subset 2), and these are clear and definitive evidence of the interaction.
Takemura
H
H
Department of Chemistry, Faculty of Science, Kyushu University, Ropponmatsu 4-2-1, Chuo-ku, Fukuoka, 810-8560 Japan.
Nakashima
S
S
Kon
N
N
Yasutake
M
M
Shinmyozu
T
T
Inazu
T
T