On the mechanism of the reaction of a magnesium( i ) complex with CO 2 : a concerted type of pathway - INSA Toulouse - Institut National des Sciences Appliquées de Toulouse Access content directly
Journal Articles Chemical Communications Year : 2014

On the mechanism of the reaction of a magnesium( i ) complex with CO 2 : a concerted type of pathway

Abstract

Theoretical mechanistic calculations (DFT) on the reactivity of [{(DipNacnac)Mg}2] (DipNacnac = [(DipNCMe)2CH]−, Dip = C6H3iPr2-2,6) towards CO2 were carried out in order to rationalise the experimental formation of a carbonate (major product) and an oxalate (minor product). Despite its apparent similarity to f-element reactivity, the magnesium(I) bimetallic complex yields the carbonate through a concerted type of pathway rather than via a transient oxo-bridged intermediate. The latter is destabilised due to the electrostatic repulsion between the two magnesium centres. The small energy barrier difference between carbonate and oxalate formation (∼10 kcal mol−1) may allow for the experimentally observed reactivity to be tuned by changing the sterics and/or electronic properties of the magnesium(I) complex.
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Dates and versions

hal-01969555 , version 1 (04-01-2019)

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  • HAL Id : hal-01969555 , version 1

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Christos E. Kefalidis, Andreas Stasch, Cameron Jones, Laurent Maron. On the mechanism of the reaction of a magnesium( i ) complex with CO 2 : a concerted type of pathway. Chemical Communications, 2014, 50 (82), pp.12318-12321. ⟨hal-01969555⟩
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