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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
Author(s) -
Brookes Nigel J.,
Graham David C.,
Christian Gemma,
Stranger Robert,
Yates Brian F.
Publication year - 2009
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21199
Subject(s) - oniom , chemistry , steric effects , ligand (biochemistry) , amide , molybdenum , reaction coordinate , density functional theory , computational chemistry , singlet state , molecule , stereochemistry , inorganic chemistry , excited state , organic chemistry , atomic physics , biochemistry , physics , receptor
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