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

Abstract

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)][Fe III (TpivPP)(C 6 HF 4 S) 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 [Fe III (TpivPP)(C 6 HF 4 S) 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.

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