MOLECULAR-COMPLEXES OF IODINE WITH METAL ACETYLACETONATES

The ability of metal acetylacetonates to act as electron donors and form molecular complexes with I2 was studied by examining the electronic, vibrational, and NMR spectra of the complexes. The specific compounds used in the study were Al(acac)3 Sc(acac)3 Zr(acac)4, and Th(acac)4. The electronic spectra of mixtures of the metal acetylacetonates with I2 in CHCl3 had, in addition to the absorption peaks characteristic of the free components, two peaks that were due to the charge transfer complexes. For each complex, the highest wavelength peak (near 360 nm) was assigned to the blue shifted I2 band, while the lower peak (between 270 nm and 305 nm) was attributed to the intermolecular charge transfer. In the i.r. spectra of each complex, the major effect of complexation was to cause the I2 stretching frequency to appear between 145 cm-1 and 160 cm-1. The positions of the absorption peaks in both the electronic and vibrational spectra led to the conclusion that in these complexes, I2 had received a large amount of charge from the donors. Complex formation had little effect on the NMR spectra of the donors. Association constants of 1:1 complexes were determined from the concentration dependence of the absorbance of the blue shifted I2 bands. Values of ΔHdg and ΔS°298 for the complex formation were obtained from the temperature variation of the association constants. The data indicate that the complexes are extremely stable species. Both the stability of the complexes and the high degree of charge transfer were rationalized by considering a model for the intermolecular interactions that involved two M(acac) rings simultaneously transferring charge from one donor to an I2 molecule. © 1990.