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In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
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In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
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A tetravalent cerium complex containing a Ce=O bond.

Yat-Ming So1, Guo-Cang Wang, Yang Li

  • 1Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong (China).

Angewandte Chemie (International Ed. in English)
|January 10, 2014
PubMed
Summary

Researchers synthesized a novel cerium(IV) oxo complex, a first for lanthanides. This cerium oxo complex displays unique oxidizing and nucleophilic reactivity, stabilized by hydrogen bonding in its solid state.

Keywords:
ceriumcrystal structuredensity functional calculationsmultiple bonds

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Area of Science:

  • Organometallic Chemistry
  • Lanthanide Chemistry
  • Inorganic Chemistry

Background:

  • Terminal oxo complexes are well-documented for transition and actinide elements.
  • Analogous lanthanide oxo complexes have not been previously reported.
  • This highlights a gap in the understanding of lanthanide reactivity.

Purpose of the Study:

  • To report the synthesis and structure of a novel cerium(IV) oxo complex.
  • To investigate the structural and electronic properties of this unique lanthanide complex.
  • To explore the reactivity of the synthesized cerium oxo complex.

Main Methods:

  • Synthesis of the cerium(IV) oxo complex.
  • X-ray crystallography for structural determination.
  • Density Functional Theory (DFT) calculations for electronic structure analysis.

Main Results:

  • A novel cerium(IV) oxo complex, [Ce f8feO(LOEt )2 (H2 O)] cdot MeC(O)NH2 (1), was successfully synthesized and structurally characterized.
  • The complex features a short Ce f8feO bond (1.857(3) 2005 Å).
  • DFT calculations revealed that hydrogen bonding to acetamide stabilizes the Ce f8feO moiety in the solid state.

Conclusions:

  • This study reports the first example of a terminal lanthanide oxo complex.
  • The cerium(IV) oxo complex exhibits significant oxidizing and nucleophilic reactivity.
  • The findings open new avenues for exploring lanthanide-based catalysts and reagents.