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Density functional theory; ketene; lithium carbenoid.

A computational study for the [2 + 1] addition of the lithium carbenoids LiCH₂X (X = Cl, Br, I) with ketene have been investigated by means of the B3LYP hybrid density functional method. All the reactions examined displayed similar concerted mechanisms for the cyclopropanation of these reagents. The lithium carbenoids react with ketene via an asynchronous attack on one CH₂ or C group of ketene with relatively low barrier to reaction in the range of 25.34-33.74 kJ/mol in THF solvent. The trend of the lithium carbenoids reaction barrier with ketene is LiCH₂Cl < LiCH₂Br < LiCH₂I. The results show that the reactions could be highly chemical reactivity with low barriers and could be favoured in experiment. The reactions could proceed easily at lower temperature. The computational results are briefly compared to other carbenoid reactions and related species.

Xing Hui Zhang¹ Fu Long Zhang¹ Zhi Yuan Geng²

1. College of Chemical Engineering, Gansu Lianhe University, Lanzhou 730010, P.R. China
2. College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, P.R. China

Published

May 2010

Manuscript received

4 May 2009

Manuscript revised

18 January 2010

Accepted

22 January 2010

• SI363-369.pdf