Vibrational spectra of complexes of cyclic imines with zinc(II) and cadmium(II)
The IR and Raman spectra of 13 complexes of ethylenimine, trimethylenlmine, pyrrolidine, and piperidine with salts of Zn(II) and Cd(II) were investigated in the region of 4000-60 cm−1. An assignment of the vibrations of the coordinated ligands (symmetry Cs) was proposed.
With increasing size of the coordinated ring, the frequency of the valence vibration v NH drops, which is explained by a decrease in the s-character of the orbital participating in the formation of the N-H bond.
In complexes with composition 3∶1, the third ligand molecule evidently exists on account of a hydrogen bond with the other two coordinated molecules.
On the basis of data on the longwave spectra, hypotheses were advanced on the structure of the investigated complexes, and the values of the metal-ligand force constants were found.
The frequencies of the metal-nitrogen valence vibrations in complexes of piperidine are substantially higher than those in complexes of the remaining imines.
KeywordsHydrogen Zinc Hydrogen Bond Cadmium Piperidine
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