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The Influence of Peripheral Ligand Bulk on Nitrogen Activation by Three-Coordinate Molybdenum Complexes-A Theoretical Study Using the ONIOM Method

journal contribution
posted on 2023-05-17, 02:05 authored by Brookes, NJ, Graham, DC, Christian, G, Stranger, R, Brian YatesBrian Yates
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.

Funding

Australian Research Council

History

Publication title

Journal of Computational Chemistry

Volume

30

Issue

13

Pagination

2146-2156

ISSN

0192-8651

Department/School

School of Natural Sciences

Publisher

John Wiley & Sons Inc

Place of publication

111 River St, Hoboken, USA, Nj, 07030

Repository Status

  • Restricted

Socio-economic Objectives

Expanding knowledge in the chemical sciences

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