51 Synthesis and Reactivity of 9-Vertex Iridium-Monocarborane Cage Complexes

Wednesday, November 4, 2009
Ballroom A+B (Camino Real Hotel)
Robin A. McCown , Department of Chemistry and Biochemistry, Baylor University, Waco, TX
Thomas D. McGrath , Department of Chemistry and Biochemistry, Baylor University, Waco, TX
F. Gordon A. Stone , Department of Chemistry and Biochemistry, Baylor University, Waco, TX

Reaction of the cation {Ir(PEt3)n}+, generated in situ, with the monocarborane anion [closo-1-CB7H8] results in oxidative insertion, with the iridium fragment becoming a cluster vertex. This reaction yields two distinct, neutral, 9-vertex {IrCB7} cluster products, depending on the reactant ratio of phosphine to iridium.   The iridium atoms in these species have differing oxidation states, demonstrating the exceptional ability of the smaller anionic monocarborane ligands to stabilize metals in higher oxidation states. These products can interconvert, via addition or removal of one phosphine ligand, and will react with halogens or with other donors to give further products with novel structures.

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