| Autor: |
Wu, Zunyi, Xiang, Chuyue, Zhang, Yutong, Song, Zhijun, Lei, Qunfang, Fang, Wenjun, Xie, Hujun |
| Předmět: |
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| Zdroj: |
Computational & Theoretical Chemistry; Aug2018, Vol. 1138, p91-98, 8p |
| Abstrakt: |
The mechanisms for the reactions of the coordinatively unsaturated iridium methylene complex Ir CH 2 [N(SiMe 2 CH 2 PPh 2 ) 2 ] with a variety of small molecules including H 2 , PMe 3 , CO, Al 2 Me 6 , and CH 3 I have been investigated by the density functional theory (DFT) calculations. The calculation results showed that the reaction of methylene complex with H 2 generates the trihydride amine IrH 3 [HN(SiMe 2 CH 2 PPh 2 ) 2 ] via a series of oxidative addition and reductive elimination steps. The reaction of methylene complex with PMe 3 produces the square planar complex Ir(PMe 3 )[N(SiMe 2 CH 2 PPh 2 ) 2 ] and CH 2 PMe 3 , 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)[(CH 2 PPh 2 CH 2 SiMe 2 NSiMe 2 CH 2 PPh 2 )] by the formation of C P bond. The reactions of methylene complex with Al 2 Me 6 and methyl iodide were also examined, and the oxidative addition step can afford a metal–carbon bond that undergoes a C C 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. [ABSTRACT FROM AUTHOR] |
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