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

journal contribution
posted on 2023-05-17, 07:57 authored by Brookes, NJ, Alireza AriafardAlireza Ariafard, Stranger, R, Brian YatesBrian Yates
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.

Funding

Australian Research Council

History

Publication title

Dalton Transactions

Volume

40

Issue

20

Pagination

5569-5578

ISSN

1477-9226

Department/School

School of Natural Sciences

Publisher

Royal Society of Chemistry

Place of publication

Thomas Graham House, Science Park, Milton Rd, Cambridge, England, Cambs, Cb4 0Wf

Rights statement

Copyright 2011 Royal Society of Chemistry

Repository Status

  • Restricted

Socio-economic Objectives

Expanding knowledge in the chemical sciences

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