About: Tetraphenylporphyrin is a research topic. Over the lifetime, 2119 publications have been published within this topic receiving 41941 citations.
Papers published on a yearly basis
TL;DR: The climax of this strategy of catalysis boosting by means of Coulombic stabilization of the initial Fe0-CO2 adduct is reached when four positively charged trimethylanilinium groups are introduced at the ortho positions of the TPP phenyls.
Abstract: The starting point of this study of through-space substituent effects on the catalysis of the electrochemical CO2-to-CO conversion by iron(0) tetraphenylporphyrins is the linear free energy correlation between through-structure electronic effects and the iron(I/0) standard potential that we established separately. The introduction of four positively charged trimethylanilinium groups at the para positions of the tetraphenylporphyrin (TPP) phenyls results in an important positive deviation from the correlation and a parallel improvement of the catalytic Tafel plot. The assignment of this catalysis boosting effect to the Coulombic interaction of these positive charges with the negative charge borne by the initial Fe0–CO2 adduct is confirmed by the negative deviation observed when the four positive charges are replaced by four negative charges borne by sulfonate groups also installed in the para positions of the TPP phenyls. The climax of this strategy of catalysis boosting by means of Coulombic stabilization...
TL;DR: In this article, the effect of electronegative bromine substituents at the peripheral positions of the porphyrin has been quantitatively analyzed by using the four-orbital approach of Gouterman.
Abstract: The free-base octabromotetraphenylporphyrin (H2OBP) has been prepared by a novel bromination reaction of (meso-tetraphenylporphyrinato)copper(II). The metal [V(IV)O, Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Ag(II), Pt(II)] derivatives exhibit interesting electronic spectral features and electrochemical redox properties. The electron-withdrawing bromine substituents at the pyrrole carbons in H2OBP and M(OBP) derivatives produce remarkable red shifts in the Soret (50 nm) and visible bands (100 nm) of the porphyrin. The low magnitude of protonation constants (pK3 = 2.6 and pK4 = 1.75) and the large red-shifted Soret and visible absorption bands make the octabromoporphyrin unique. The effect of electronegative bromine substituents at the peripheral positions of the porphyrin has been quantitatively analyzed by using the four-orbital approach of Gouterman. A comparison of MO parameters of MOBP derivatives with those of the meso-substituted tetraphenylporphyrin (M(TPP)) and unsubstituted porphine (M(P)) derivatives provides an explanation for the unusual spectral features. The configuration interaction matrix element of the M(OBP) derivatives is found to be the lowest among the known substituted porphyrins, indicating delocalization of ring charge caused by the increase in conjugation of p orbitals of the bromine onto the ring orbitals. The electron-transfer reactivities of the porphyrins have been dramatically altered by the peripheral bromine substituents, producing large anodic shifts in the ring and metal-centered redox potentials. The increase in anodic shift in the reduction potential of M(OBP)s relative to M(TPP)s is found to be large (550 mV) compared to the shift in the oxidation potential (300 mV). These shifts are interpreted in terms of the resonance and inductive interactions of the bromine substituents.
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