POLYNUCLEAR HYDROXO COMPLEXES.
Final scientific rept. 1 Oct 64-30 Sep 68,
MINNESOTA UNIV MINNEAPOLIS DEPT OF CHEMISTRY
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The hydrolytic condensation reactions of several organometallic compounds were studied in detail. Among the systems examined were CH32SnIV, CH32GaIII, CH32AuIII and CH33PtIV. It was found that the presence of alkyl groups in the first coordination sphere of metal ions labilizes the remaining ligands to a very great degree. This is especially apparent with the classically inert PtIV species where the average lifetime of a bound water molecule of CH33PtOH23 was found. Both the exchange rate and the hydration number of this cation were determined with Oxygen-17 n.m.r. The ion CH32Au was shown with Raman spectroscopy to have the cis structure in aqueous solutions. The thermodynamics of the condensation reaction were examined in solution at 25C, and the end product was found to be CH32AuOH4. A complete crystal structure determination was made for this compound. Because the lability of these complexes leads to very fast reactions, the rates were too high to be determined using flow systems. The hydrogen isotope effect on the acid dissociation of CoNH35OH23 was examined and found to be normal, and the acid dissociation of coordinated water molecules does not seem to give rise to anomalous isotope effects. Author
- Inorganic Chemistry