A molecular orbital rationalization of ligand effects in N2 activation |
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Authors: | Ariafard Alireza Brookes Nigel J Stranger Robert Yates Brian F |
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Affiliation: | School of Chemistry, University of Tasmania, Private Bag 75, Hobart TAS 7001, Australia. ariafard@yahoo.com |
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Abstract: | Molecular orbital theory has been used to study a series of [(micro-N2){ML3}2] complexes as models for dinitrogen activation, with M=Mo, Ta, W, Re and L=NH2, PH2, AsH2, SbH2 and N(BH2)2. The main aims of this study have been to provide a thorough electronic analysis of the complexes and to extend previous work involving molecular orbital analyses. Molecular orbital diagrams have been used to rationalize why for L=NH2 ligand rotation is important for the singlet state but not the triplet, to confirm the effect of ligand pi donation, and to rationalize the importance of the metal d-electron configuration. The outcomes of this study will assist with a more in-depth understanding of the electronic basis for N2 activation and allow clearer predictions to be made about the structure and multiplicity of systems involved in transition-metal catalysis. |
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Keywords: | density functional calculations ligand rotation molecular orbital theory nitrogen activation reaction mechanisms |
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