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A thorium metallacyclopentadiene complex: a combined experimental and computational study.

Bo Fang1, Guohua Hou, Guofu Zi

  • 1Department of Chemistry, Beijing Normal University, Beijing 100875, China. gzi@bnu.edu.cn dcfang@bnu.edu.cn.

Dalton Transactions (Cambridge, England : 2003)
|April 1, 2015
PubMed
Summary

Researchers synthesized the first thorium metallacyclopentadiene complex. Its unique reactivity with diazoalkanes and azides forms novel six- and seven-membered organometallic complexes.

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Area of Science:

  • Organometallic Chemistry
  • Thorium Chemistry
  • Main Group Chemistry

Background:

  • Thorium organometallic chemistry is less explored than other early transition metals.
  • Metallacyclopentadienes are versatile building blocks in inorganic synthesis.

Purpose of the Study:

  • To synthesize and characterize a novel thorium metallacyclopentadiene complex.
  • To investigate the electronic structure and bonding of the complex using DFT.
  • To explore the reactivity of the thorium metallacyclopentadiene with different organic reagents.

Main Methods:

  • Synthesis via reduction of a thorium precursor with potassium graphite in the presence of diphenylacetylene.
  • Structural characterization (details not provided in abstract).
  • Density Functional Theory (DFT) calculations to probe electronic structure and bonding.

Main Results:

  • Successful synthesis of the first thorium metallacyclopentadiene complex, (η(5)-C5Me5)2Th(η(2)-C4Ph4).
  • DFT studies indicate significant involvement of thorium 5f orbitals in the Th-metallacyclopentadiene bonding.
  • The complex exhibits distinct reactivity compared to thorium metallacyclopropenes, yielding six- and seven-membered heterocyclic complexes upon reaction with diazoalkanes and azides.

Conclusions:

  • The study reports the first synthesis and characterization of a thorium metallacyclopentadiene.
  • The electronic structure reveals important 5f orbital participation in bonding.
  • The unique reactivity profile opens new avenues for synthesizing complex thorium-containing heterocyclic compounds.