The influence of peripheral ligand bulk on nitrogen activation by three-coordinate molybdenum complexes-a theoretical study using the ONIOM method

Nigel J. Brookes, David C. Graham, Gemma Christian, Robert Stranger, Brian F. Yates

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    25 Citations (Scopus)

    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 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.

    Original languageEnglish
    Pages (from-to)2146-2156
    Number of pages11
    JournalJournal of Computational Chemistry
    Volume30
    Issue number13
    DOIs
    Publication statusPublished - Oct 2009

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