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Isomerism in Complexes
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Ions are atoms or molecules bearing an electrical charge. A cation (a positive ion) forms when a neutral atom loses one or more electrons from its valence shell, and an anion (a negative ion) forms when a neutral atom gains one or more electrons in its valence shell. Compounds composed of ions are called ionic compounds (or salts), and their constituent ions are held together by ionic bonds: electrostatic forces of attraction between oppositely charged cations and anions. 
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Iron(II) Corrole Anions.

Kenneth P Caulfield1, Jeanet Conradie2,3, Hadi D Arman1

  • 1Department of Chemistry , University of Texas at San Antonio , San Antonio , Texas 78249 , United States.

Inorganic Chemistry
|November 8, 2019
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This study reports the first isolated divalent iron corrole complex, K(THF)2[FeII(TPC)]. This iron(II) corrole exhibits intermediate spin and undergoes reactions with CO, O2, and alkyl electrophiles.

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Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Coordination Chemistry

Background:

  • Corrole complexes are important in catalysis and bioinorganic chemistry.
  • Divalent iron complexes are less explored compared to other oxidation states.
  • Understanding the electronic structure and reactivity of iron corroles is crucial for their applications.

Purpose of the Study:

  • To synthesize and characterize the first isolated divalent iron corrole complex.
  • To investigate the electronic properties and spin state of the iron(II) corrole.
  • To explore the reactivity of the divalent iron corrole with various ligands and electrophiles.

Main Methods:

  • Synthesis of K(THF)2[FeII(TPC)] via reduction of [Fe(TPC)(THF)] with KC8.
  • Crystallographic characterization of the iron(II) corrole complex.
  • Density functional theory (DFT) calculations (OLYP, B3LYP) to determine electronic configurations.
  • Reactions with carbon monoxide, oxygen, and organic electrophiles (e.g., iodomethane).

Main Results:

  • Isolation and crystallographic characterization of K(THF)2[FeII(TPC)], the first divalent iron corrole complex.
  • The complex exhibits an intermediate-spin state (S = 1) with square-planar geometry.
  • DFT calculations suggest two nearly equienergetic d-electron configurations for the [FeII(TPC)]- anion.
  • Reactions yield a low-spin iron(II) carbonyl complex, a transient oxygen adduct, and iron(III)/iron(IV) species upon electrophilic attack.
  • The first instance of alkyl ligand coordination to an iron corrole complex ([Fe(TPC)Me]) was achieved.

Conclusions:

  • The successful synthesis and characterization of the divalent iron corrole complex open new avenues in iron corrole chemistry.
  • The electronic structure and reactivity studies provide fundamental insights into the behavior of iron in the +2 oxidation state within a corrole ligand.
  • This work lays the foundation for developing novel iron corrole-based catalysts and functional materials.