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Related Concept Videos

Crystal Field Theory - Octahedral Complexes02:58

Crystal Field Theory - Octahedral Complexes

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...
Valence Bond Theory02:42

Valence Bond Theory

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...
Complexation Equilibria: The Chelate Effect01:19

Complexation Equilibria: The Chelate Effect

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...
Colors and Magnetism03:02

Colors and Magnetism

Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human eye.
Metal-Ligand Bonds02:51

Metal-Ligand Bonds

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...
Crystal Field Theory - Tetrahedral and Square Planar Complexes02:46

Crystal Field Theory - Tetrahedral and Square Planar Complexes

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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Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
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Entropy-Driven Ligand Exchange in a Rotationally Flexible Dinuclear Fe(II)-Fe(II) Complex.

Pablo G Porta1, Benjamin Kintzel2, Birgit Weber2

  • 1Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, Ulm 89081, Germany.

Inorganic Chemistry
|June 17, 2026
PubMed
Summary
This summary is machine-generated.

This study reports the first di-iron complex with a flexible ligand, revealing an entropy-driven equilibrium. The complex

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Synthesis of Triazole and Tetrazole-Functionalized Zr-Based Metal-Organic Frameworks Through Post-Synthetic Ligand Exchange

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Area of Science:

  • Coordination Chemistry
  • Bioinorganic Chemistry
  • Catalysis

Background:

  • Metalloenzymes utilize precise metal-metal distances and coordination environments for catalysis.
  • Mimicking these features in homogeneous systems is challenging, especially capturing transient coordination events.

Purpose of the Study:

  • To explore the first di-iron complex with a novel rotationally flexible dinucleating ligand.
  • To characterize an unexpected, entropy-driven ligand-exchange equilibrium.

Main Methods:

  • Variable temperature studies in solution.
  • Single-crystal X-ray diffraction for structural characterization.
  • In silico mechanistic studies using density functional theory (DFT).
  • Electrochemical analysis.

Main Results:

  • The ligand's central C-C bond allows adaptation to varying metal-metal distances.
  • Cooling induces a reversible color change (green to blue) due to chlorido ligand substitution by methanol.
  • DFT calculations indicate entropy drives this ligand exchange upon cooling.
  • Electrochemical analysis shows a reversible redox event at -0.05 V vs Fc/Fc+ and irreversible reductions.

Conclusions:

  • The characterized di-iron complex exhibits unique ligand flexibility and an entropy-driven equilibrium.
  • The complex's redox properties are comparable to known iron catalysts, suggesting potential catalytic applications.