Issue 20, 2011

Tuning the Laplaza-Cummins 3-coordinate M[N(R)Ph]3catalyst to activate and cleave CO2

Abstract

The Laplaza-Cummins catalyst L3Mo (L = N(R)Ar), is experimentally inactive towards carbon dioxide. Previous theoretical analysis identified the cause for this inactivity and suggested that a switch to a d2 transition metal may induce activity towards the inert CO2 molecule. In this manuscript we have tested this hypothesis by altering the central metal to Ta, Nb or V. Our calculations suggest that the tantalum analogue, TaL3, will successfully bind to CO2 in a mononuclear η2 arrangement and, importantly, will strongly activate one C–O bond to a point where spontaneous C–O cleavage occurs. This prediction of a strongly exothermic reaction takes into consideration the initial barrier to formation, spin crossings, ligand bulk and even the choice of density functional in the calculations. The Nb analogue will likely coordinate CO2 but reaction may not proceed further. In contrast, the V analogue faces an initial coordination barrier and is not expected to be sufficiently active to coordinate CO2 to the triamide catalyst. A similar scenario exists for mixed metal interactions involving a d2 and d4 combination in a bridging dinuclear arrangement.

Graphical abstract: Tuning the Laplaza-Cummins 3-coordinate M[N(R)Ph]3 catalyst to activate and cleave CO2

Supplementary files

Article information

Article type
Paper
Submitted
07 Jan 2011
Accepted
24 Mar 2011
First published
14 Apr 2011

Dalton Trans., 2011,40, 5569-5578

Tuning the Laplaza-Cummins 3-coordinate M[N(R)Ph]3 catalyst to activate and cleave CO2

N. J. Brookes, A. Ariafard, R. Stranger and B. F. Yates, Dalton Trans., 2011, 40, 5569 DOI: 10.1039/C1DT10026B

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