Electronic structure methods have been combined with the ONIOM approach to carry out a comprehensive study of the effect of ligand bulk on the activation of dinitrogen with three-coordinate molybdenum complexes. Calculations were performed, with both density functional and CCSD(T) methods. Our results show that not only is there expected destabilisation of the intermediate on the pathway due to direct steric interactions of the bulky groups, but also there is significant electronic destabilisation as the size of the ligand increases. This latter destabilization is due to the inability of the molecule to accommodate a rotated amide group bound to the molybdenum, once the amide reaches a certain size. This destabilization also leads to a clear preference for the triplet intermediate (rather than the singlet intermediate) for bulky substituents which is in agreement with experiment. Overall, the calculated reaction profile for the bulky substituents shows a good, correlation with the available experimental data. © 2009 Wiley Periodicals, Inc.

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
Author:	Brookes, NJ (Dr Nigel Brookes)
Author:	Graham, DC (Dr David Graham)
Author:	Yates, BF (Professor Brian Yates)
ID Code:	62451
Year Published:	2009
Funding Support:	Australian Research Council (DP0986529)
Web of Science® Times Cited:	18
Deposited By:	Chemistry
Deposited On:	2010-03-12
Last Modified:	2010-04-12
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