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Coordination Number and Geometry02:57

Coordination Number and Geometry

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For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
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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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The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
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Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
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Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
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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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Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates
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Trigonal prismatic metal complexes: a not so rare coordination geometry?

Leighton J Alcock1, Germán Cavigliasso2, Anthony C Willis2

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Summary

This study determined the solid-state structures of metal complexes with a hexaamine macrobicyclic ligand, revealing an exact trigonal prismatic geometry. Theoretical calculations confirm this geometry is most stable for specific metal electron configurations.

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Area of Science:

  • Coordination Chemistry
  • Inorganic Chemistry
  • Structural Chemistry

Background:

  • Hexaamine macrobicyclic ligands are known to form stable metal complexes.
  • Trigonal prismatic geometry is less common than octahedral or tetrahedral geometries in coordination chemistry.

Purpose of the Study:

  • To determine the solid-state structures of two metal complexes featuring a specific hexaamine macrobicyclic ligand.
  • To investigate the preferred coordination geometry of this ligand with various metal ions.
  • To computationally validate the stability of the observed geometry.

Main Methods:

  • Single-crystal X-ray diffraction was used to determine the solid-state structures.
  • Theoretical calculations (e.g., density functional theory) were employed to assess geometric stability.

Main Results:

  • The solid-state structures of two metal complexes were successfully determined.
  • Both complexes exhibit an exact trigonal prismatic coordination geometry around the metal ion.
  • Theoretical calculations indicate that trigonal prismatic geometry is the most stable configuration for d(0), d(10), and high-spin d(5) metal complexes with this ligand, provided M-N bond distances exceed approximately 2.35 Å.

Conclusions:

  • The hexaamine macrobicyclic ligand enforces an exact trigonal prismatic geometry on metal ions in the solid state.
  • This specific geometry is theoretically predicted to be highly stable for certain electronic configurations of metal ions coordinated by this ligand.