Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Circular Dichroism of Chromium(III) Complexes. IX. Circular Dichroism Spectra and Stereochemistry of Dinitritobis(diamine)chromium(III) Complexes
Sumio Kaizaki
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1983 Volume 56 Issue 12 Pages 3625-3631

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Abstract

The circular dichroism (CD) spectra of optically active dinitritobis(diamine)chromium(III) complexes were measured in the visible and near-ultraviolet region, where the diamines used were ethylenediamine, trimethylenediamine, (R)-propylenediamine, (1R, 2R)-1,2-cyclohexanediamine, (2R, 4R)- and (2R, 4S)-2,4-pentanedianiine. The stereochemistry and the conformational (rotational) isomerism of coordinated nitrito ligands were discussed on the basis of the solvent-dependent CD spectra in the near-ultraviolet region of an intraligand absorption band localized on nitrito ligands. It is proposed that the CD variation in the intraligand transition region among the complexes concerned is responsible for the chiral arrangement of nitrito ligands. Further, the conformation of trimethylenediamine chelate in the trans-dinitrito-(R)-propylenediamine complex is determined to take a chair form in comparison with the CD behavior of the corresponding (2R, 4S)-2,4-pentanediainine complex.

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