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This lesson delves into the geometry of a radical, which is influenced by the electronic structure of the molecule. The principle is similar to that of a lone pair, where the unpaired electron influences the geometry at the radical center.
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Persistent four-coordinate iron-centered radical stabilized by π-donation.

Yusuke Sunada1, Shintaro Ishida2, Fumiya Hirakawa2

  • 1Institute for Materials Chemistry and Engineering , Kyushu University , 6-1 Kasugakoen , Kasuga , Fukuoka 816-8580 , Japan.

Chemical Science
|August 1, 2017
PubMed
Summary

A novel dinuclear iron carbonyl complex with an unsupported Fe-Fe bond was synthesized. This complex generates a reactive iron radical, which readily forms new iron complexes upon reaction with organic radicals.

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Area of Science:

  • Organometallic Chemistry
  • Inorganic Chemistry
  • Radical Chemistry

Background:

  • Dinuclear iron carbonyl complexes are important in catalysis.
  • Unsupported metal-metal bonds present unique reactivity.
  • Iron-centered radicals offer novel reaction pathways.

Purpose of the Study:

  • Synthesize a dinuclear iron carbonyl complex with an unsupported Fe-Fe bond.
  • Investigate the thermal homolysis of the Fe-Fe bond.
  • Characterize the resulting iron radical and its reactivity.

Main Methods:

  • Reaction of Fe2(CO)9 with phosphinyl radical 1.
  • Thermal treatment to induce Fe-Fe bond homolysis.
  • Spectroscopic characterization of intermediates and products.

Main Results:

  • Synthesis of dinuclear iron carbonyl complex 2 with an elongated unsupported Fe-Fe bond.
  • Generation of a four-coordinate iron-centered radical (3) via thermal homolysis.
  • Demonstration of radical 3's high reactivity with organic radicals, forming diamagnetic five-coordinate Fe(ii) complexes.

Conclusions:

  • The synthesized dinuclear iron complex provides a route to novel iron radicals.
  • The iron radical is stabilized by pi-donation and exhibits high reactivity.
  • This work expands the understanding of iron-metal bond reactivity and radical chemistry.