The Isomers of the Bis(Diethylenetriamine)Chromium(III) and Bis[Di(3-Aminopropyl)Amine]Chromium(III) Cations, [Cr(Dien)2]3+ and [Cr(Dpt)2]3+: Preparation and Characterization

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Abstract
Addition of dien in slight excess to CrCl3.6H2O in Me2SO (which has been dehydrated at 190�C, then cooled to 170�) produces an isomeric mixture of orange-yellow [Cr( dien )2] Cl3.Me2SO of � approximate composition mer 70%; s- fac 30%; u- fac 98% mer ) mixture. All three isomers can be obtained as (Hg2Cl7)3- salts, suitable for single-crystal X-ray analysis, and the cation geometries have been established from these X-ray data. The mer and s- fac isomers are distinguished by their different labilities in acidic solution ( mer is relatively inert, s- fac decomposes rapidly), their different infrared and visible absorption spectra, and their different chromatographic behaviour on SP- Sephadex C-25. However, this latter technique failed to detect the u- fac form and was complicated by the facile decomposition of the s- fac isomer. The mer and s- fac forms isomerize rapidly in Me2SO and the equilibrium is largely towards the mer. [Cr( dpt )2]Cl3 [ dpt = di(3- aminopropyl )amine] could be obtained only by direct reaction between anhydrous CrCl3 and dpt , and was subsequently precipitated as the iodide and perchlorate salts. These consisted entirely of the mer isomer, from their isomorphism with the corresponding mer -[Cr( dpt )2 ]3+ salts. The six-membered rings in -[Cr( dien )2 ]3+ are considerably more resistant to hydrolytic decomposition than the rings in mer -[ cr ( dien )2]3+ and mer -[Co( dpt )2]3+.

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