The influence of peripheral ligand bulk on nitrogen activation by three‐coordinate molybdenum complexes—A theoretical study using the ONIOM method |
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Authors: | Nigel J Brookes David C Graham Gemma Christian Robert Stranger Brian F Yates |
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Institution: | 1. School of Chemistry, University of Tasmania, Private Bag 75, Hobart, Tasmania 7001, Australia;2. Department of Chemistry, The Australian National University, Canberra ACT 0200, Australia |
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Abstract: | 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 destabilization of the intermediate on the pathway due to direct steric interactions of the bulky groups, but also there is significant electronic destabilization 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. J Comput Chem 2009 |
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Keywords: | nitrogen activation transition metal complexes ligand bulk steric and electronic destabilization molecular orbital theory |
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