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. I. L-Tartrato Complexes. Their Stereospecific Formation and Spin-forbidden Absorption Bands
Sumio KaizakiJinsai HidakaYoichi Shimura
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1969 Volume 42 Issue 4 Pages 988-994

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Abstract

Two novel mixed chromium (III) complexes containing L-tartrates and 2,2′-dipyridyl or 1,10-phenanthroline have been prepared, and their electronic absorption and circular dichroism spectra and the rotatory dispersion have been measured in the region of near-infrared to ultraviolet. From the construction of molecular models and from the comparison of the CD bands of the present complexes with those of the resolved oxalato complexes, (−)546-K[Cr(ox)2(dip)]·3H2O and (−)546-K[Cr(ox)2(phen)]·4H2O, it has been concluded that the present complexes have a binuclear structure in which two Cr(III) ions are bridged by two tetradentate L-tartrato ligands and that the absolute configuration of the binuclear complexes is Λ(C2)-Λ(C2). Their formation is completely stereospecific and their formulae are represented by Ba[Cr2(L-tart2H)(dip)2]2·9H2O and NH4[Cr2(L-tart2H)(phen)2]·6.5H2O. The absolute configurations of several complexes which commonly belong to a general type, cis-[Cr(O)4(N)2] have been determined on the basis of circular dichroism studies of the present binuclear complexes. The circular dichroism in the spin-forbidden absorption band region have also been measured and discussed.

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