TY - JOUR
T1 - A theoretical study of the photochemical reductive elimination and thermal oxidative addition of molecular hydrogen from and to the Ir-complex
AU - Hayashi, Y.
AU - Nakai, H.
AU - Tokita, Y.
AU - Nakatsuji, H.
PY - 1998/6
Y1 - 1998/6
N2 - 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.
AB - 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.
KW - Configuration interaction method
KW - Excited states
KW - Iridium complexes
KW - Photochemical reductive elimination of H
KW - Symmetry adapted cluster (SAC)/SAC
KW - Thermal oxidative addition of H
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U2 - 10.1007/s002140050327
DO - 10.1007/s002140050327
M3 - Article
AN - SCOPUS:0032105203
VL - 99
SP - 210
EP - 214
JO - Theoretical Chemistry Accounts
JF - Theoretical Chemistry Accounts
SN - 1432-881X
IS - 4
ER -