The reactivity of coordinatively unsaturated iridium methylene complex IrCH2[N(SiMe2CH2PPh2)2]: A quantum chemistry study

Publication date: 15 August 2018Source: Computational and Theoretical Chemistry, Volume 1138Author(s): Zunyi Wu, Chuyue Xiang, Yutong Zhang, Zhijun Song, Qunfang Lei, Wenjun Fang, Hujun XieAbstractThe mechanisms for the reactions of the coordinatively unsaturated iridium methylene complex IrCH2[N(SiMe2CH2PPh2)2] with a variety of small molecules including H2, PMe3, CO, Al2Me6, and CH3I have been investigated by the density functional theory (DFT) calculations. The calculation results showed that the reaction of methylene complex with H2 generates the trihydride amine IrH3[HN(SiMe2CH2PPh2)2] via a series of oxidative addition and reductive elimination steps. The reaction of methylene complex with PMe3 produces the square planar complex Ir(PMe3)[N(SiMe2CH2PPh2)2] and CH2PMe3, and the latter can further react with methylene complex to give ethene. The reaction of methylene complex with CO results in the formation of Ir(CO)[(CH2PPh2CH2SiMe2NSiMe2CH2PPh2)] by the formation of CP bond. The reactions of methylene complex with Al2Me6 and methyl iodide were also examined, and the oxidative addition step can afford a metal–carbon bond that undergoes a CC bond forming migratory insertion to ultimately lead to the formation of ethene. Present study can provide new insights into the reactivity of transition metal methylene complex.Graphical abstract

Source: Computational and Theoretical Chemistry - July 6, 2018 Category: Chemistry Source Type: research