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At high magnetic fields the 128.8 MHz (195)Pt NMR of all the species in the series [PtCl(n)(H(2)O)(6-n)](4-n) (n = 2-6) display unique (35/37)Cl isotope effects resulting in a unique 'fine-structure' of each individual resonance, which constitutes an unambiguous spectroscopic 'fingerprint' characteristic of the structure of the octahedral platinum(IV) complex, provided (195)Pt NMR are recorded at optimum magnetic field homogeneity and carefully controlled temperature (293 ± 0.1 K). The detailed (195)Pt resonance fine-structure observed experimentally can readily be accounted for by an isotopologue and isotopomer model for each complex, showing particularly noticeable differences between stereoisomer pairs such as the cis/trans- and fac/mer-complexes. Moreover partial isotopic (18)O enrichment of the coordinated water molecules in the series [Pt(35/37)Cl(n)(H(2)(16/18)O)(6-n)](n-2) (n = 2-6) confirms this model. This technique can thus be considered a novel, direct spectroscopic method of chemical speciation of appropriate platinum(IV) complexes in solution without reference to accurate chemical shifts of authentic members of such a series. These effects are interpreted qualitatively in terms of the high sensitivity of (195)Pt NMR shielding to very small and subtle Pt-(35/37)Cl and Pt-(16/18)OH(2) bond displacements. Preliminary work shows this also applied to the corresponding bromido-complexes.

A kinetic study of [OsO(4)] reduction by aliphatic alcohols (MeOH and EtOH) was performed in a 2.0 M NaOH matrix at 298.1 K. The rate model that best fitted the UV-VIS data supports a one-step, two electron reduction of Os(VIII) (present as both the [Os(VIII)O(4)(OH)](-) and cis-[Os(VIII)O(4)(OH)(2)](2-) species in a ratio of 0.34:0.66) to form the trans-[Os(VI)O(2)(OH)(4)](2-) species. The formed trans-[Os(VI)O(2)(OH)(4)](2-) species subsequently reacts relatively rapidly with the cis-[Os(VIII)O(4)(OH)(2)](2-) complex anion to form a postulated [Os(VII)O(3)(OH)(3)](2-) species according to: cis-[Os(VIII)O(4)(OH)(2)](2-) + trans-[Os(VI)O(2)(OH)(4)](2-) (k+2) <−> (k-2) 2[Os(VII)O(3)(OH)(3)](2-). The calculated forward, k(+2), and reverse, k(-2), reaction rate constants of this comproportionation reaction are 620.9 ± 14.6 M(-1) s(-1) and 65.7 ± 1.2 M(-1) s(-1) respectively. Interestingly, it was found that the postulated [Os(VII)O(3)(OH)(3)](2-) complex anion does not oxidize MeOH or EtOH. Furthermore, the reduction of Os(VIII) with MeOH or EtOH is first order with respect to the aliphatic alcohol concentration. In order to corroborate the formation of the [Os(VII)O(3)(OH)(3)](2-) species predicted with the rate model simulations, several Os(VIII)/Os(VI) mole fraction and mole ratio titrations were conducted in a 2.0 M NaOH matrix at 298.1 K under equilibrium conditions. These titrations confirmed that the cis-[Os(VIII)O(4)(OH)(2)](2-) and trans-[Os(VI)O(2)(OH)(4)](2-) species react in a 1:1 ratio with a calculated equilibrium constant, K(COM), of 9.3 ± 0.4. The ratio of rate constants k(+2) and k(-2) agrees quantitatively with K(COM), satisfying the principle of detailed balance. In addition, for the first time, the molar extinction coefficient spectrum of the postulated [Os(VII)O(3)(OH)(3)](2-) complex anion is reported.

A detailed analysis of the (35)Cl/(37)Cl isotope shifts induced in the 128.8 MHz (195)Pt NMR resonances of [PtCl(n)(H(2)O)(6 - n)](4 - n) complexes (n = 6,5,4) in acidic solution at 293 K, shows that the unique isotopologue and isotopomer distribution displayed by the resolved (195)Pt resonances, serve as a fingerprint for the unambiguous identification and assignment of the isotopic stereoisomers of [PtCl(5)(H(2)O)](-) and cis/trans-[PtCl(4)(H(2)O)(2)].

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