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Crystal Field Theory - Octahedral Complexes02:58

Crystal Field Theory - Octahedral 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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Valence Bond Theory02:42

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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Crystal Field Theory - Tetrahedral and Square Planar Complexes02:46

Crystal Field Theory - Tetrahedral and Square Planar Complexes

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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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Ionic Bonding and Electron Transfer02:48

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Ions are atoms or molecules bearing an electrical charge. A cation (a positive ion) forms when a neutral atom loses one or more electrons from its valence shell, and an anion (a negative ion) forms when a neutral atom gains one or more electrons in its valence shell. Compounds composed of ions are called ionic compounds (or salts), and their constituent ions are held together by ionic bonds: electrostatic forces of attraction between oppositely charged cations and anions. 
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Exceptions to the Octet Rule02:55

Exceptions to the Octet Rule

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Many covalent molecules have central atoms that do not have eight electrons in their Lewis structures. These molecules fall into three categories:
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Radicals: Electronic Structure and Geometry01:07

Radicals: Electronic Structure and Geometry

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This lesson delves into the geometry of a radical, which is influenced by the electronic structure of the molecule. The principle is similar to that of a lone pair, where the unpaired electron influences the geometry at the radical center.
Accordingly, the structure of a trivalent radical lies between the geometries of carbocations and carbanions. An sp2-hybridized carbocation is trigonal planar, while an sp3-hybridized carbanion is trigonal pyramidal. Here, the difference in geometry is...
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Updated: Oct 29, 2025

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
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Electronic Structure of Superoxidized Radical Cationic Dodecaborate-Based Clusters.

Bo Li1, Xinglong Zhang1, Julia M Stauber2

  • 1Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.

The Journal of Physical Chemistry. A
|July 9, 2021
PubMed
Summary

Researchers explored the reversible redox behavior of boron clusters, specifically B12(OR)12. They identified and isolated the superoxidized radical cationic form, [B12(OR)12]•+, for the first time, revealing tunable redox potentials.

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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Computational Chemistry

Background:

  • Boron clusters exhibit diverse structures and unique bonding, attracting significant theoretical interest.
  • Perfunctionalized boron clusters, such as B12(OR)12, are key subjects in cluster chemistry research.
  • Understanding redox properties is crucial for exploring new functionalities of boron clusters.

Purpose of the Study:

  • To investigate the generality of a newly discovered reversible redox event in perfunctionalized B12(OR)12 clusters.
  • To characterize the superoxidized radical cationic form, [B12(OR)12]•+.
  • To elucidate the electronic and structural changes associated with the redox process.

Main Methods:

  • Comprehensive theoretical studies using (Time-Dependent) Density Functional Theory ((TD-)DFT).
  • Electrochemical experiments to probe redox potentials and stability.
  • Analysis of spin density distribution and partial charges.

Main Results:

  • The reversible redox behavior and the isolation of the [B12(OR)12]•+ species were confirmed for various perfunctionalized B12(OR)12 clusters.
  • Spin density in the radical cations is delocalized in the boron core, while supporting groups gain positive partial charges.
  • Oxidation potentials are tunable by modifying the electronic properties of the supporting R groups.

Conclusions:

  • The identified redox event is general across perfunctionalized B12(OR)12 clusters, offering a pathway for tuning their electrochemical properties.
  • The [B12(OR)12]•+ species exhibit characteristic absorption spectra due to mixed local/charge-transfer excitations.
  • This work expands the understanding of boron cluster chemistry and their potential applications in redox-active materials.