eCite Digital Repository

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


Brookes, NJ and Ariafard, A and Stranger, R and Yates, BF, Tuning the Laplaza-Cummins 3-coordinate M[N(R)Ph]3 catalyst to activate and cleave CO2, Dalton Transactions, 40, (20) pp. 5569-5578. ISSN 1477-9226 (2011) [Refereed Article]

Restricted - Request a copy

Copyright Statement

Copyright 2011 Royal Society of Chemistry

DOI: doi:10.1039/c1dt10026b


The Laplaza-Cummins catalyst L(3)Mo (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 d(2) transition metal may induce activity towards the inert CO(2) 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, TaL(3), will successfully bind to CO(2) in a mononuclear eta(2) 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 CO(2) 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 CO(2) to the triamide catalyst. A similar scenario exists for mixed metal interactions involving a d(2) and d(4) combination in a bridging dinuclear arrangement.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Organometallic chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Brookes, NJ (Dr Nigel Brookes)
UTAS Author:Ariafard, A (Associate Professor Alireza Ariafard)
UTAS Author:Yates, BF (Professor Brian Yates)
ID Code:72713
Year Published:2011
Funding Support:Australian Research Council (DP0986529)
Web of Science® Times Cited:8
Deposited By:Chemistry
Deposited On:2011-08-31
Last Modified:2017-10-25

Repository Staff Only: item control page