Inertness of the [Re6Se5Cl3]5+ cluster core to substitution by OH- in organic solutions: synthesis, structural and liquid secondary ion mass spectroscopy characterization of K(H2O)2[Re6Se5Cl9] and (n-Bu4N)[Re6Se5Cl9] and the crystal structure of (n-Bu4N)2[Re6Se6Cl8

Abstract

When ethanol solutions of K[Re6Se5Cl9] are allowed to crystallize, the compound formulated K(H2O)2[Re6Se5Cl9] (1) is obtained. Extensive characterization, which includes chemical analysis, X-ray structure determination and liquid secondary ion mass spectrometry (LSIMS), supports this formulation, which differs from that proposed earlier, K[Re6Se5(OH)2Cl7]·H2O. This conclusively demonstrates that no substitution of an inner μ-core halogen by OH− occurs within the cluster core. This is discussed and shown to be fully consistent with the present well-documented chemistry, which requires that substitutions of halogen by divalent elements only are allowed. The paper is complemented by the crystal structures of (n-Bu4N)[Re6Se5Cl9] and (n-Bu4N)2[Re6Se6Cl8], which had not yet been properly reported.