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Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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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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Atomic Layer Deposition of Vanadium Dioxide and a Temperature-dependent Optical Model
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A well-defined terminal vanadium(III) oxo complex.

Amanda E King1, Michael Nippe, Mihail Atanasov

  • 1Department of Chemistry, University of California , Berkeley, California 94720-1460, United States.

Inorganic Chemistry
|August 7, 2014
PubMed
Summary
This summary is machine-generated.

Researchers synthesized and characterized a stable vanadium(III) oxo complex, a long-sought species in inorganic chemistry. This breakthrough advances understanding of low-valent vanadyl chemistry and opens new avenues for research.

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Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Coordination Chemistry

Background:

  • Vanadium oxo complexes in V+ and IV+ oxidation states are well-understood.
  • Stable terminal mononuclear vanadium(III) oxo complexes have been theoretically predicted but experimentally elusive.
  • Ligand-field theory suggests stability for V(III) oxo species.

Purpose of the Study:

  • To synthesize and characterize a well-defined terminal mononuclear vanadium(III) oxo complex.
  • To investigate the reactivity and electronic properties of this novel V(III) oxo species.
  • To explore implications for low-valent vanadyl chemistry.

Main Methods:

  • Synthesis of a vanadium(III) oxo complex using a pentadentate polypyridyl ligand (PY5Me2).
  • Characterization of the vanadium(III) oxo species through spectroscopic and analytical techniques.
  • Experimental and computational studies on the reactivity and electronic structure.

Main Results:

  • Successful isolation and characterization of a stable, terminal mononuclear vanadium(III) oxo complex, [V(III)(O)(PY5Me2)](+).
  • The V(III) oxo species is unreactive towards H- and O-atom transfer but reacts with protons.
  • Computational studies predict ligand-based reduction upon further electron reduction, despite pyridine's poor π-accepting nature.

Conclusions:

  • The synthesis represents a significant advancement in stabilizing low-valent vanadium oxo species.
  • The characterized V(III) oxo complex provides a platform for studying fundamental reactivity.
  • Findings pave the way for isolating and investigating even lower-valent vanadyl species, such as V(II) oxo complexes.