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A Molecular Orbital Rationalization of Ligand Effects in N 2 Activation
Author(s) -
Ariafard Alireza,
Brookes Nigel J,
Stranger Robert,
Yates Brian F
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200800235
Subject(s) - molecular orbital , singlet state , non bonding orbital , chemistry , electron configuration , ligand (biochemistry) , fragment molecular orbital , computational chemistry , metal , molecular orbital diagram , molecular orbital theory , electronic structure , transition metal , homo/lumo , catalysis , crystallography , molecule , physics , atomic physics , excited state , organic chemistry , ion , biochemistry , receptor
Molecular orbital theory has been used to study a series of [(μ‐N 2 ){ML 3 } 2 ] complexes as models for dinitrogen activation, with M=Mo, Ta, W, Re and L=NH 2 , PH 2 , AsH 2 , SbH 2 and N(BH 2 ) 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=NH 2 ligand rotation is important for the singlet state but not the triplet, to confirm the effect of ligand π 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 N 2 activation and allow clearer predictions to be made about the structure and multiplicity of systems involved in transition‐metal catalysis.