Chemistry Viewed through New Eyes: What New Secrets Can

Although some of the platinum(II/IV) and rhodium(III) chemistry is considered ‘old’ and wellknown, the application of modern multinuclear NMR spectroscopic methods to this chemistry in solution reveals new details about their rich and relevant solution chemistry. In this paper we will briefly illustrate that the highly-sensitive 195 Pt NMR shielding is an excellent probe to explore aspects such as solvation, ion-pairing, and the hydrolysis chemistry of inter alia [PtCl6-n(H2O)n] n-2 (n=0-5). Moreover the novel use of 35 Cl/ 37 Cl and 18 O isotopes effects as unique NMR ’fingerprints’ leading to a new and unambiguous method of chemical speciation of the numerous possible Pt II/IV and Rh III complexes present in halide-rich aqueous solutions. In the case of Rh(III) chemistry a new, direct speciation distribution diagram has been established for [RhCln(H2O)6-n] 3-n complexes (n = 3-6) in HCl solution at 292 K with these methods.