By Colin D. Hubbard Rudi Van Eldik
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Extra resources for Advances in Inorganic Chemistry: Inorganic Reaction Mechanisms (AIC) (Advances in Inorganic Chemistry)
A. DUNAND et al.
6 kJ molÀ1 for Rh3+ (132) (Fig. 8). The strong Rh^O bonds constrains water exchange on [Rh(H2O)6]3+ to proceed via an Ia mechanism, whereas the same reaction on [Ru(H2O)6]2+, which has considerably weaker Ru^O bonds, follows the Id or D mechanism. The low-spin t52g [Ru(H2O)6]3+ is four orders of magnitude more labile than the t62g [Ru(H2O)6]2+ and exchanges water by an Ia mechanism (125). The slow water exchange on both complexes allowed the direct measurement of the electron exchange of the [Ru(H2O)6]3+/2+ couple in acidic solution (Eq.
The approach of a seventh water molecule towards a face or edge of the coordination octahedron is electrostatically disfavored by the ¢lled t2g orbitals which are spread out between the ligands. Rate constants for anation reactions of ClÀ, BrÀ, and IÀ on [Ru(H2O)6]2+ are very similar, indicating identical steps to reach the transition state, namely the dissociation of a water molecule (130). 2 Ia I (129) (129) a SOLVENT EXCHANGE ON METAL IONS [M(solvent)6]2+ Rate constant for the exchange of a particular coordinated solvent molecule (6 ).
Advances in Inorganic Chemistry: Inorganic Reaction Mechanisms (AIC) (Advances in Inorganic Chemistry) by Colin D. Hubbard Rudi Van Eldik