Assisted Crystallization of Organometallic Cations by Interplay with Inorganic Anionic Clusters Units: Synthesis and Characterizations of the [Cp*(dppe)Fe–NCMe]2·M6L14 Series (M6L14 = Cluster Unit: [Re6S6Br8]2–, [Mo6Br14]2– and [Mo6I14]2–)

Abstract

AbstractNovel hybrid inorganic/organometallic compounds have been obtained from the crystallization of inorganic anionic clusters units with the [Cp*(dppe)Fe–NCMe]+organometallic entity as the cationic counter part. After dissolution of Cs2M6L14 (M6L14 = [Re6S6Br8]2–, [Mo6Br14]2– and [Mo6I14]2–) and [Cp*(dppe)Fe–NCMe]Cl precursors in acetonitrile at room temperature, the reaction proceeds by a metathesis of the Cl– anion by [M6L14]2– anions and precipitation of CsCl. The crystal structures of the [Cp*(dppe)Fe–NCMe]2[M6L14] series reveal that inorganic and organic entities can be assembled without any structural modifications to both partners whatever the M6L14 unit. These properties of the M6L14 cluster units could be extended for the crystallization of other novel organometallic cations when usual small counter anions do not lead to any crystallization with the new organometallic cation (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)