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Valence Bond Theory

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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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Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
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The periodic table arranges atoms based on increasing atomic number so that elements with the same chemical properties recur periodically. When their electron configurations are added to the table, a periodic recurrence of similar electron configurations in the outer shells of these elements is observed. Because they are in the outer shells of an atom, valence electrons play the most important role in chemical reactions. The outer electrons have the highest energy of the electrons in an atom...
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Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.
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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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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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Updated: Jul 18, 2025

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
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Planar pentacoordinate s-block metals.

Meng-Hui Wang1, Amlan J Kalita2, Mesías Orozco-Ic3

  • 1Institute of Atomic and Molecular Physics, Jilin University Changchun 130023 China zcui@jlu.edu.cn sudip@jlu.edu.cn.

Chemical Science
|August 25, 2023
PubMed
Summary
This summary is machine-generated.

Planar pentacoordinate s-block metals are stabilized by sigma-delocalization, not pi-bonds. These clusters exhibit sigma-aromaticity, challenging traditional criteria for planar hypercoordination.

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Area of Science:

  • Quantum Chemistry
  • Materials Science
  • Inorganic Chemistry

Background:

  • Planar hypercoordination typically requires delocalized pi-bonds.
  • Electropositive elements usually do not form planar hypercoordinate structures.

Purpose of the Study:

  • To investigate if sigma-delocalization can stabilize planar pentacoordinate s-block metals.
  • To explore the aromaticity of such sigma-delocalized systems.

Main Methods:

  • High-level ab initio computations were employed.
  • Analysis of electronic structure and magnetic properties was performed.

Main Results:

  • Singlet D5h structures with planar pentacoordinate metals (Li, Mg, Ca, Sr) were found to be the global minima.
  • These clusters, composed of electropositive elements, exhibit sigma-aromaticity, fulfilling Hückel's rule with six sigma-electrons.
  • A diatropic ring current and strong magnetic shielding were observed in response to an external magnetic field.

Conclusions:

  • Sigma-delocalization, through multicenter sigma-bonds, is sufficient to stabilize planar pentacoordinate s-block metals.
  • These findings expand the understanding of planar hypercoordination and aromaticity beyond traditional pi-electron systems.