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Related Concept Videos

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

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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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Bonding in Metals02:32

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Metallic bonds are formed between two metal atoms. A simplified model to describe metallic bonding has been developed by Paul Drüde called the “Electron Sea Model”. 
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Crystal Field Theory - Tetrahedral and Square Planar Complexes02:46

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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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Metal-Ligand Bonds02:51

Metal-Ligand Bonds

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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.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
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Complexation Equilibria: The Chelate Effect01:19

Complexation Equilibria: The Chelate Effect

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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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Related Experiment Video

Updated: Sep 18, 2025

Quantitative Atomic-Site Analysis of Functional Dopants/Point Defects in Crystalline Materials by Electron-Channeling-Enhanced Microanalysis
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Vacancy-Induced Atomic Diffusion in a Molecular Metal Cluster Complex.

Tetsuro Murahashi1, Kosuke Iwata1, Koshi Miyazawa1

  • 1Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Institute of Science Tokyo, O-okayama, Meguro-ku, Tokyo, 152-8552, Japan.

Angewandte Chemie (International Ed. in English)
|June 26, 2025
PubMed
Summary

Atomic vacancies in molecules enable atom migration, demonstrating vacancy-induced dynamics in discrete palladium clusters. This study reveals rapid palladium atom self-diffusion within a Pd12 cluster complex.

Keywords:
Atomic diffusionAtomic vacancyDynamic behaviorMetal clustersOrganometallic compounds

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Quantitative Atomic-Site Analysis of Functional Dopants/Point Defects in Crystalline Materials by Electron-Channeling-Enhanced Microanalysis
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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Physical Chemistry

Background:

  • Atomic vacancies in bulk materials facilitate atom migration and dynamics.
  • The behavior of vacancies and induced atomic dynamics in discrete molecular clusters remains largely unexplored.

Purpose of the Study:

  • To investigate vacancy-induced atomic dynamics in a discrete molecular cluster.
  • To synthesize and characterize a palladium cluster complex with an atomic vacancy.
  • To observe and understand the diffusion of palladium atoms within the cluster.

Main Methods:

  • Synthesis of a close-packed Pd12 cluster complex with a palladium-atom vacancy.
  • Variable-temperature Nuclear Magnetic Resonance (NMR) spectroscopy.
  • X-ray structure analysis.
  • Theoretical calculations.

Main Results:

  • Generation of a Pd12 cluster complex exhibiting a Pd-atom vacancy.
  • Observation of rapid diffusion of palladium atoms within the cluster.
  • Identification of the atomic vacancy at surface sites of the Pd12 core, migrating rapidly on the NMR timescale.
  • Demonstration of low-energy barrier self-diffusion for all surface palladium atoms.

Conclusions:

  • Atomic diffusion via the vacancy mechanism is possible within discrete molecular entities.
  • The study provides the first evidence of vacancy-induced dynamics in a molecular cluster.
  • This finding opens new avenues for understanding and controlling atomic motion in nanoscale systems.