Bis(2,3,5,6‐tetrafluorothiophenolato) Iron(III) (α,α,α,β)‐Tetrakis(o–pivalamidophenyl)porphyrin Ion Complex: Synthesis, Spectroscopic, Structural Characterization and Computational Studies

Abstract

In this work, we present the synthesis of the cryptand‐222)potassium bis(2,3,5,6‐tetrafluorothiophenolato)[α,α,α,β‐tetrakis(o‐pivalamidophenyl) porphyrinato]iron(III) with the formula [K(cryp‐222)][FeIII(TpivPP)(C6HF4S)2] (I). Notably, we started with the (α,α,α,α) atropisomer and the final product is made by the (α,α,α,β) atropisomer as shown by the X‐ray molecular structure of complex I. The crystal structure of our P450 model indicates that the mean equatorial distance between the central ion and the four nitrogen atoms of the pyrrole ring of the porphyrin (Fe−Np) is equal to 1.997(6) Å indicating that complex I is a ferric low‐spin complex (S=1/2). Both X‐ray molecular structure and Hirshfeld surface analysis show that the crystal packing of I is made by C−H⋅⋅⋅O and C−H⋅⋅⋅F weak intermolecular hydrogen interactions involving neighboring [FeIII(TpivPP)(C6HF4S)2]− ion complexes. Furthermore, the characteristics of the HOMO and LUMO molecular frontier orbitals and the reactivity of complex I were investigated by DFT/B3LYP/LanL2DZ level of DFT and a Molecular Electrostatic Potential (MEP) calculation has been made to determine the nucleophilic‐electrophilic of this new ferric metalloporphyrin.