The structure and coordination chemistry of boron porphyrin complexes B2OX2 (TpYPP) (X = OH, F; Y = Cl, CH3) in connection with its chemical reactivity are analyzed atab initio density functional theory B3LYP/6-31G* and restricted Hartree-Fock RHF/6-31G* levels of theory. Global reactivity and local selectivity descriptors are used as adequate tools to analyze the isomerism effect (Z orE isomer) and the substitution effect (X: in axial ligand; or Y: in porphyrin ligand). In all the cases, we find that theE conformation is the most stable one, in agreement with X-ray results, and that a principle of maximum hardness in the isomerism analysis is fullfilled. In the substitution analysis, we find that the three global reactivity indexes (η, Ω, ϰ) and the two local reactivity indexes (fk, electrostatic potential) used in this paper predict the same trend when an electron-withdrawing substituent is replaced by an electron donor. Finally, we show that substitution in the porphyrin ligand is slightly more significant than that in the axial ligand.
Volume 135, 2023
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