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Terminal end‐on coordination of dinitrogen versus isoelectronic CO : A comparison using the charge displacement analysis
Author(s) -
Schmitt Manuel,
Krossing Ingo
Publication year - 2023
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.26837
Subject(s) - chemistry , valence (chemistry) , natural bond orbital , covalent bond , copper , formal charge , crystallography , atomic orbital , computational chemistry , electrostatics , density functional theory , electron , organic chemistry , physics , quantum mechanics
The metal dinitrogen bonding in a wide series of terminal end‐on dinitrogen complexes is investigated with the charge displacement analysis based on natural orbitals of chemical valence (CD‐NOCV). The effect of the σ donation and π backdonation on the NN bond are discussed and compared with the observations for a series of carbonyl complexes, published in 2016 by Tarantelli et al. The σ donation is relative invariant over the series of dinitrogen complexes and has no significant effect on the NN bond strength, whereas the π backdonation causes a considerable elongation of the NN bond. Some uncommon examples of weakly bound dinitrogen with blue‐shifted stretching frequency compared to free N 2 ( ν = 2330 cm −1 ) are known. The dinitrogen bonding in these complexes is simulated with a point charge. Apparently, electrostatics account for the shortened N─N bond in these systems.