Assisted Crystallization of Organometallic Cations by Interplay with Inorganic Anionic Clusters Units: Synthesis and Characterizations of the [Cp*(dppe)Fe–NCMe] 2 ·M 6 L 14 Series (M 6 L 14 = Cluster Unit: [Re 6 S 6 Br 8 ] 2– , [Mo 6 Br 14 ] 2– and [Mo 6 I 14 ] 2– )

Novel 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 Cs 2 M 6 L 14 (M 6 L 14 = [Re 6 S 6 Br 8 ] 2– , [Mo 6 Br 14 ] 2– and [Mo 6 I 14 ] 2– ) and [Cp*(dppe)Fe–NCMe]Cl precursors in acetonitrile at room temperature, the reaction proceeds by a metathesis of the Cl – anion by [M 6 L 14 ] 2– anions and precipitation of CsCl. The crystal structures of the [Cp*(dppe)Fe–NCMe] 2 [M 6 L 14 ] series reveal that inorganic and organic entities can be assembled without any structural modifications to both partners whatever the M 6 L 14 unit. These properties of the M 6 L 14 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)