Reversible Carbon-Carbon Double Bond Cleavage of a Ketene Ligand at a Single Iridium(I) Center: A Theoretical Study

摘要

Modeling the chemistry of ketene complex {k~2-(t-Bu)_2PCH_2P(t-Bu)_2}IrCl[#eta#~2-(C,C)-Ph_2C=C=O] (1), DFT studies have been carried out for (k~2-H_2PCH_2PH_2)IrCl[#eta#~2-(C,C)-H_2C=C=O](A), for cation (k~2-H_2PCH_2PH_2)Ir[#eta#~2-(C,C)-CH_2=C=O]~+ (B), for its carbene carbonyl isomer (k~2-H_2PCH_2PH_2)Ir(CH_2)(CO)~+(C), and for their interconversion by intramolecular C=C double bond cleavage/formation.