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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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Planar Pentacoordinate Zinc Group Elements Stabilized by Multicentric Bonds.

Amlan J Kalita1, Indrani Baruah1, Kangkan Sarmah1

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Inorganic Chemistry
|January 10, 2022
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Computational studies reveal stable planar pentacoordinate zinc group elements (Zn, Cd, Hg) in Li5M+ clusters. These structures are stabilized by multicentric bonds and electron donation, leading to negative oxidation states for the central metal atom.

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Area of Science:

  • Computational chemistry
  • Inorganic chemistry
  • Quantum chemistry

Background:

  • Pentacoordinate structures are common for main group elements.
  • Exploring novel bonding motifs and electronic structures in metal clusters is crucial for understanding chemical bonding.
  • Zinc group elements (Zn, Cd, Hg) typically exhibit higher coordination numbers.

Purpose of the Study:

  • To investigate the possibility of planar pentacoordinate structures for zinc group elements (Zn, Cd, Hg).
  • To determine the stability and electronic properties of such proposed structures.
  • To explore the role of alkali metal frameworks in stabilizing unusual coordination geometries.

Main Methods:

  • Density Functional Theory (DFT) calculations were employed.
  • Global minimum searches were performed to identify stable isomers.
  • Natural Population Analysis (NPA) was used to determine oxidation states.

Main Results:

  • Planar pentacoordinate structures for Li5M+ (M = Zn, Cd, Hg) were found to be at a global minimum.
  • The stability of these clusters is attributed to multicentric bonding interactions.
  • The central zinc group element adopts a negative oxidation state due to electron donation from the Li5+ framework.
  • Similar planar pentacoordinate structures were also identified in Na5Zn+ and Na5Cd+ clusters.

Conclusions:

  • Planar pentacoordinate geometries are achievable for zinc group elements within specific alkali metal cluster environments.
  • Multicentric bonding plays a key role in stabilizing these unusual structures.
  • The electronic environment provided by the alkali metal framework can induce negative oxidation states in the central metal atom.