Remote substituent effects on homolytic Fe‐N bond energies of p‐G‐C6H4NHFe(CO)2(η5‐C5H5) and p‐G‐C6H4(COMe)NFe(CO)2(η5‐C5H5) studied using Hartree–Fock and density functional theory methods
Copyright policy )Remote substituent effects on homolytic Fe‐N bond energies of p‐G‐C6H4NHFe(CO)2(η5‐C5H5) and p‐G‐C6H4(COMe)NFe(CO)2(η5‐C5H5) studied using Hartree–Fock and density functional theory methods
The nature and strength of metal–ligand bonds in organotransition–metal complexes is crucial to the understanding of organometallic reactions and catalysis. The Fe‐N homolytic bond dissociation energies [ΔHhomo(Fe‐N)′s] of two series of para‐substituted Fp anilines p‐G‐C6H4NHFp [1] and p‐G‐C6H4N(COMe)Fp [2] were studied using the Hartree–Fock (HF) and the density functional theory methods with large basis sets. In this study, Fp is (η5‐C5H5)Fe(CO)2 and G are NO2, CN, COMe, CO2Me, CF3, Br, Cl, F, H, Me, MeO and NMe2. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and accurate predictions of ΔHhomo(Fe‐N)′s. B3LYP can also satisfactorily predict the α and remote substituent effects on ΔHhomo(Fe‐N)′s [ΔΔHhomo(Fe‐N)′s]. The good correlations [r = 0.96 (g, 1), 0.99(g, 2)] of ΔΔHhomo(Fe‐N)′s in series 1 and 2 with the substituent σp+ constants imply that the para‐substituent effects on ΔHhomo(Fe‐N)′s originate mainly from polar effects, but those on radical stability originate from both spin delocalization and polar effects. ΔΔHhomo(Fe‐N)′s(1,2) conform to the captodative principle. Insight from this work may help the design of more effective catalytic processes. Copyright © 2012 John Wiley & Sons, Ltd.
- University of Saskatchewan Canada
- Beijing University of Chinese Medicine China (People's Republic of)
- Nankai University China (People's Republic of)
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