35Cl/ 37Cl isotope effects in 103Rh NMR of [RhCl n(H 2O) 6-n] 3-n complex anions in hydrochloric acid solution as a unique 'NMR finger-print' for unambiguous speciation

Geswindt T.E. ; Gerber W.J. ; Brand D.J. ; Koch K.R. (2012)


A detailed analysis of the 35Cl/ 37Cl isotope effects observed in the 19.11MHz 103Rh NMR resonances of [RhCl n(H 2O) 6-n] 3-n complexes (n=3-6) in acidic solution at 292.1K, shows that the 'fine structure' of each 103Rh resonance can be understood in terms of the unique isotopologue and in certain instances the isotopomer distribution in each complex. These 35Cl/ 37Cl isotope effects in the 103Rh NMR resonance of the [Rh 35/37Cl 6] 3- species manifest only as a result of the statistically expected 35Cl/ 37Cl isotopologues, whereas for the aquated species such as for example [Rh 35/37Cl 5(H 2O)] 2-, cis-[Rh 35/37Cl 4(H 2O) 2] - as well as the mer-[Rh 35/37Cl 3(H 2O) 3] complexes, additional fine-structure due to the various possible isotopomers within each class of isotopologues, is visible. Of interest is the possibility of the direct identification of stereoisomers cis-[RhCl 4(H 2O) 2] -, trans-[RhCl 4(H 2O) 2] -, fac-[RhCl 3(H 2O) 3] and mer-[RhCl 3(H 2O) 3] based on the 103Rh NMR line shape, other than on the basis of their very similar δ( 103Rh) chemical shift. The 103Rh NMR resonance structure thus serves as a novel and unique 'NMR-fingerprint' leading to the unambiguous assignment of [RhCl n(H 2O) 6-n] 3-n complexes (n=3-6), without reliance on accurate δ( 103Rh) chemical shifts. © 2012 Elsevier B.V.

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