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

研究成果: Article査読

1 被引用数 (Scopus)

抄録

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.

本文言語English
ページ(範囲)210-214
ページ数5
ジャーナルTheoretical Chemistry Accounts
99
4
DOI
出版ステータスPublished - 1998 6

ASJC Scopus subject areas

  • 物理化学および理論化学

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