PlatinumII/IV And RhodiumIII Chemistry Viewed Through New Eyes: What New Secrets Can 195Pt And 103Rh NMR Spectroscopy Reveal About Speciation As Relevant To Refining Solutions?

Although some of the platinum(II/IV) and rhodium(III) chemistry is considered ?old? and well-known, 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 195Pt 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 35Cl/37Cl and 18O isotopes effects as unique NMR ?fingerprints? leading to a new and unambiguous method of chemical speciation of the numerous possible PtII/IV and RhIII 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.