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Vinylic C−H Bond Activation and Hydrogenation Reactions of Tp‘Ir(C2H4)(L) Complexes

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Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas, Campus de Cantoblanco, 28049 Madrid, Spain, Departamento de Química y Ciencia de los Materiales, Universidad de Huelva, 21819 Palos de la Frontera, Huelva, Spain, and Departamento de Química InorgánicaInstituto de Investigaciones Químicas, Universidad de Sevilla-Consejo Superior de Investigaciones Científicas, c/ Américo Vespuccio s/n, Isla de la Cartuja, 41092 Sevilla, Spain
Cite this: Inorg. Chem. 1998, 37, 18, 4538–4546
Publication Date (Web):August 11, 1998
Copyright © 1998 American Chemical Society

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    The substitution of one of the ethylene ligands of the complexes Tp‘Ir(C2H4)2 (Tp‘ = TpMe2, 1*; Tp‘ = Tp, 1) by soft donors such as tertiary phosphines or carbon monoxide is a facile reaction that gives the corresponding Tp‘Ir(C2H4)(L) adducts. Spectroscopic studies support their formulation as five-coordinate, 18-electron species that possess a distorted trigonal bipyramidal geometry. This proposal has been confirmed by a single-crystal X-ray study carried out with the PMe2Ph complex TpMe2Ir(C2H4)(PMe2Ph) (3b*). Related hydride derivatives of Ir(III) can be obtained either by hydrogenation of the Ir(I) adducts (in general, this gives Tp‘IrH2(L) compounds) or by thermal activation of one of the C−H bonds of the coordinated C2H4 ligand of the TpMe2Ir(C2H4)(L) compounds. All these reactions can be understood by invoking the participation of transient, 16-electron (η2-Tp‘)Ir intermediates, but the thermodynamics of the [Ir](C2H4) to [Ir]H(CHCH2) conversion does not require an overall change in the coordination mode of the Tp‘ ligand.

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     Instituto de Ciencia de Materiales de Madrid, CSIC.

     Universidad de Huelva.


    In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.


     Universidad de Sevilla-CSIC.

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