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Issue 42, 2009
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Reactivity of CO2 towards Mo[N(R)Ph]3

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Abstract

The Laplaza/Cummins L3Mo (L = N(R)Ar) system is a very important complex for activating small molecules such as N2. Previous experimental work has shown that CS2 binds to the L3Mo system and forms an Mo–CS–Mo intermediate, while the environmentally important CO2 molecule is unreactive. The aim of this paper is to explain why there is this contrast in reactivity. We have used density functional methods to show that at first glance the reaction of 3L3Mo + CO2 should proceed smoothly to give L3Mo–O + L3Mo–CO–MoL3. However initial coordination of the CO2 molecule to L3Mo does not take place because of the bending of CO2, the energy required to cross from the doublet to the quartet state, and the lower metal–CO2 binding energy compared to metal–CS2. The subsequent formation of the L3Mo–CO–MoL3 intermediate is similarly unfeasible due to steric and entropic effects. We have provided a molecular orbital rationalization for these effects and have also shown that it is important to take account of steric factors in order to get an accurate understanding of the energetic picture.

Graphical abstract: Reactivity of CO2 towards Mo[N(R)Ph]3

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Publication details

The article was received on 20 May 2009, accepted on 19 Aug 2009 and first published on 03 Sep 2009


Article type: Paper
DOI: 10.1039/B909982D
Citation: Dalton Trans., 2009,0, 9266-9272
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    Reactivity of CO2 towards Mo[N(R)Ph]3

    N. J. Brookes, A. Ariafard, R. Stranger and B. F. Yates, Dalton Trans., 2009, 0, 9266
    DOI: 10.1039/B909982D

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