Premium
Substituent effects on gas‐phase homolytic Fe–N bond energies of m ‐G‐C 6 H 4 NHFe(CO) 2 (η 5 ‐C 5 H 5 ) and m ‐G‐C 6 H 4 N(COMe)Fe(CO) 2 (η 5 ‐C 5 H 5 ) studied using density functional theory methods
Author(s) -
Zeng Qing,
Li Zucheng,
Wang YiBo
Publication year - 2018
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3782
Subject(s) - chemistry , homolysis , substituent , cyclopentadienyl complex , density functional theory , delocalized electron , bond dissociation energy , dissociation (chemistry) , computational chemistry , crystallography , stereochemistry , catalysis , radical , organic chemistry
One of the most fundamental properties in chemistry is the bond dissociation energy, the energy required to break a specific bond of a molecule. In this paper, the Fe–N homolytic bond dissociation energies [Δ H homo (Fe–N)'s] of 2 series of (meta‐substituted anilinyl)dicarbonyl(η 5 ‐cyclopentadienyl) iron [ m ‐G‐C 6 H 4 NHFp ( 1 )] and (meta‐substituted α‐acetylanilinyl)dicarbonyl(η 5 ‐cyclopentadienyl) iron [ m ‐G‐C 6 H 4 N(COMe)Fp ( 2 )] were studied using density functional theory methods with large basis sets. In this study, Fp is (η 5 ‐C 5 H 5 )Fe(CO) 2 , and G is NO 2 , CN, COMe, CO 2 Me, CF 3 , Br, Cl, F, H, Me, MeO, and NMe 2 . The results show that Tao‐Perdew‐Staroverov‐Scuseria, Minnesota 2006, and Becke's power‐series ansatz from 1997 with dispersion corrections functionals can provide the best price/performance ratio and accurate predictions of Δ H homo (Fe–N)'s. The ΔΔ H homo (Fe–N)'s ( 1 and 2 ) conform to the captodative principle. The polar effects of the meta‐substituents show the dominant role to the magnitudes of ΔΔ H homo (Fe–N)'s. σ α · and σ c · values for meta‐substituents are all related to polar effects. Spin‐delocalization effects of the meta‐substituents in ΔΔ H homo (Fe–N)'s are small but not necessarily zero. RE plays an important role in determining the net substituent effects on Δ H homo (Fe–N)'s. Insight from this work may help the design of more effective catalytic processes.