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Breaking Chemistry's Strongest Bond: Can Three-Coordinate [M{N(R)Ar}3] Complexes Cleave Carbon Monoxide


Christian, G and Stranger, R and Petrie, S and Yates, BF and Cummins, CC, Breaking Chemistry's Strongest Bond: Can Three-Coordinate [M{N(R)Ar}3] Complexes Cleave Carbon Monoxide, Chemistry - A European Journal, 13, (15) pp. 4264-4272. ISSN 0947-6539 (2007) [Refereed Article]

DOI: doi:10.1002/chem.200601643


The reaction pathway for the interaction of CO with three-coordinate TaIII, WIII and ReIII complexes (modelled on the experimental [M{N-(tBu)Ar}3] system) has been explored by using density functional methods. Calculations show that CO binds without a barrier to [Re(NH2)3], forming the encounter complex [OC-Re-(NH 2)3], which is stabilized by ≈ 280 kJ mol-1 relative to the reactants. The binding of [Ta(NH2)3] to the oxygen terminus of CO is inhibited by a barrier of only 20 kJ mol -1 and is followed by spontaneous cleavage of the C-O bond to form the sproducts [C-Re(NH2)3] and [O-Ta(NH2) 3]. The salient features of the potential energy surface are more favourable to CO cleavage than the analogous N2 cleavage by [Mo(NH2)3], which is less exothermic (335 vs. 467 kJ mol-1) and is impeded by a significant barrier (66 kJ mol -1). The ReIII/TaIII/CO system therefore appears to be an excellent candidate for cleaving the exceptionally strong C-O bond under mild laboratory conditions. The related WIII/Ta III dimer, which significantly weakens but does not cleave the CO bond, may be a suitable alternative when the chemistry is to be performed on activated CO rather than on the strongly bound oxide and carbide cleavage products. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Transition metal chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Yates, BF (Professor Brian Yates)
ID Code:51088
Year Published:2007
Web of Science® Times Cited:22
Deposited By:Chemistry
Deposited On:2007-08-01
Last Modified:2020-12-15

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