ABSTRACT
Intrinsic and extrinsic forces behind the distortion in metal atom clusters can be readily distinguished provided that the clusters are embedded in a suitable ligand environment and that the tunneling of the protons in the peripheral ligands is then analyzed by inelastic neutron scattering. For the [Cr3 O(OOCCH3 )6 (H2 O)3 ]Clâ 6 H2 O model system studied, the tunneling process is very sensitive to the local environment. Thus a tool is available to allow a better assessment of the cause of structural distortions.
ABSTRACT
Kinetics of the overall reaction [Cr(3)O(O(2)CCH(3))(6)(H(2)O)(3)](+) + 3 urea right harpoon over left harpoon [Cr(3)O(O(2)CCH(3))(6)(urea)(3)](+) + 3H(2)O have been studied spectrophotometrically. Monophasic kinetics were observed in both directions. The reverse steps, of urea dissociation, were monitored using an analytical technique which permits direct determination of the concentration of liberated urea and does not require knowledge of extinction coefficients of intermediate species. Results imply that consecutive steps occur with rate constants in close to the statistical ratios of k(1):k(2):k(3) = 3:2:1 and k(-)(1):k(-)(2):k(-)(3) = 1:2:3. Rates indicate strong labilization of urea, compared to the case of mononuclear complex [Cr(urea)(6)](3+).