A theoretical study of the photochemical reductive elimination and thermal oxidative addition of molecular hydrogen from and to the Ir-complex

Y. Hayashi, Hiromi Nakai, Y. Tokita, H. Nakatsuji

    Research output: Contribution to journalArticle

    1 Citation (Scopus)

    Abstract

    The electronic mechanisms of the cyclic processes of photochemical reductive elimination of H2 from [IrClH2(PH3)3] and thermal oxidative addition of H2 to [IrCl(PH3)3] are investigated theoretically. The geometries of the ground and excited states are optimized using the Hartree-Fock and single excitation configuration interaction methods, respectively, and higher level calculations for the ground and excited states are carried out by the symmetry adapted cluster (SAC)/SAC-configuration interaction method. The present calculation shows that the reductive elimination of H2 from [IrClH2(PH3)3] dose not occur thermally but photochemically through diabatic conversion from the lowest A′ excited state to the ground state (A′), while the oxidative addition of H2 to [IrCl(PH3)3] easily proceeds thermally. The lowest 1A′ excited state involves the nature of the Ir-H2 antibonding.

    Original languageEnglish
    Pages (from-to)210-214
    Number of pages5
    JournalTheoretical Chemistry Accounts
    Volume99
    Issue number4
    Publication statusPublished - 1998 Jun

    Fingerprint

    Excited states
    Hydrogen
    elimination
    Ground state
    hydrogen
    excitation
    configuration interaction
    ground state
    Crystal symmetry
    symmetry
    Geometry
    Hot Temperature
    dosage
    geometry
    electronics

    Keywords

    • Configuration interaction method
    • Excited states
    • Iridium complexes
    • Photochemical reductive elimination of H
    • Symmetry adapted cluster (SAC)/SAC
    • Thermal oxidative addition of H

    ASJC Scopus subject areas

    • Physical and Theoretical Chemistry

    Cite this

    A theoretical study of the photochemical reductive elimination and thermal oxidative addition of molecular hydrogen from and to the Ir-complex. / Hayashi, Y.; Nakai, Hiromi; Tokita, Y.; Nakatsuji, H.

    In: Theoretical Chemistry Accounts, Vol. 99, No. 4, 06.1998, p. 210-214.

    Research output: Contribution to journalArticle

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