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Theoretical investigation of the stepwise hydrolysis of the [Re(3)(mu-Cl)(3)Cl(9)](3-) anion.

A detailed study of the stepwise substitution of the chloride ligands in the [Re3(mu-Cl)3Cl9](3-) (1) anion by water molecules is presented using theoretical methods. Ligand lability as well as the structure and relative stability of the various mono-[Re3(mu-Cl)3Cl8(H2O)](2-) (2a,b) and dihydro-[Re3(mu-Cl)3Cl7(H2O)2](-) (3a-f) conformers is examined. Clear preferences for the positions of the incoming water ligands are proposed based on calculated energy and vibrational data, which fully agree with the experimental results.