103Rh-NMR-Untersuchungen an Chloro-Bromo-Rhodaten(III) und Bestimmung der Stabilitätskonstanten im System [RhClnBr6-n]3-, n = 0-6 / 103Rh NMR Studies of Chloro-Bromo-Rhodates(III) and Determination of the Stability Constants in the System [RhCl„Br6-n]3-, n = 0-6

Abstract

By 103Rh NMR spectroscopy the ten compounds of the system [RhCl„Br6_„]3-, n = 0-6 are identified by separate signals. A downfield shift of approximately 160 ppm is observed per substitution of Cl by Br, and the stereoisomers for n = 2, 3, 4 are separated by at least 4 ppm. From the relative intensities of the 103Rh signals in equilibrated solutions, whose total contents of Rh. Cl and Br are known, six individual stability constants are calculated. Their product gives the overall stability constant, indicating [RhBr6]3- to be 36,300 times more stable than [RhCl6]3-. On treatment of [RhBr6]3- with HCl cis/fac isomers are formed stereospecifically, whereas the reaction of [RhCl6]3- with HBr gives trans isomers, n = 2 and 4, containing 20—30% of the cis compounds; only mer-[RhCl3Br3] 3- is obtained pure. The high resolution spectra of [RhCl6]3- and [RhBr6]3- are exhibit five signals each, reflecting the intensity patterns of the most abundant isotopomers within [Rh35Cln 37Cl6-n]3-, n = 2-6, and [Rh79Br„81Br6_„]3-, n = 1-5, respectively.