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

Y. Hayashi, H. 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
DOIs
Publication statusPublished - 1998 Jun

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

Fingerprint Dive into the research topics of 'A theoretical study of the photochemical reductive elimination and thermal oxidative addition of molecular hydrogen from and to the Ir-complex'. Together they form a unique fingerprint.

  • Cite this