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Dipnictogen f-Element Chemistry: A Diphosphorus Uranium Complex.

Jingzhen Du1, David Hunger2, John A Seed1

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|April 1, 2021
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Researchers synthesized the first uranium diphosphorus complex, a breakthrough in f-element chemistry. This discovery opens new avenues for understanding phosphorus bonding and reactivity in heavy elements.

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Area of Science:

  • Organometallic Chemistry
  • Inorganic Chemistry
  • F-element Chemistry

Background:

  • While f-element dinitrogen complexes are known, f-element diphosphorus complexes remained undiscovered.
  • Diphosphorus (P2) is a heavier congener of dinitrogen (N2), presenting unique bonding challenges.

Purpose of the Study:

  • To synthesize and characterize the first f-element diphosphorus complex.
  • To investigate the bonding and electronic structure of the uranium-diphosphorus interaction.
  • To explore the reactivity of the novel diphosphorus complex.

Main Methods:

  • Synthesis of a uranium(IV) diphosphorus complex via a phosphadibenzonorbornadiene-mediated P atom transfer.
  • Experimental characterization using spectroscopic and crystallographic techniques.
  • Computational modeling to elucidate electronic structure and bonding.

Main Results:

  • Successful synthesis of a side-on bound diphosphorus complex of uranium(IV).
  • Characterization revealed the diphosphorus ligand exists as a dianionic (P2)2- species.
  • In-plane uranium-phosphorus π-bonding dominates, with a supplementary weak δ-symmetry interaction.

Conclusions:

  • This study reports the first f-element diphosphorus complex, expanding the known chemistry of heavy group 15 elements.
  • The activated (P2)2- ligand and dominant π-bonding provide new insights into f-element-ligand interactions.
  • Preliminary reactivity studies show conversion to uranium cyclo-P3 complexes, indicating potential for generating reactive phosphido species.