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Related Concept Videos

Structural Isomerism02:34

Structural Isomerism

19.6K
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
19.6K
Stereoisomerism02:52

Stereoisomerism

12.3K
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
12.3K
¹H NMR: Long-Range Coupling01:27

¹H NMR: Long-Range Coupling

1.9K
The coupling interactions of nuclei across four or more bonds are usually weak, with J values less than 1 Hz. While these are usually not observed in spectra, the presence of multiple bonds along the coupling pathway can result in observable long-range coupling.
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene...
1.9K
Valence Bond Theory02:42

Valence Bond Theory

9.0K
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...
9.0K
Complexation Equilibria: Factors Influencing Stability of Complexes01:09

Complexation Equilibria: Factors Influencing Stability of Complexes

443
In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
443
Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)01:22

Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)

1.1K
Vicinal or three-bond coupling is commonly observed between protons attached to adjacent carbons. Here, nuclear spin information is primarily transferred via electron spin interactions between adjacent C‑H bond orbitals. This generally favors the antiparallel arrangement of spins, so 3J values are usually positive.
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the...
1.1K

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Isotopic Effect in Double Proton Transfer Process of Porphycene Investigated by Enhanced QM/MM Method
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Isomerization-Controlled Proton-Electron Coupling in a π-Planar Metal Complex.

Pingping Huang1, Yukihiro Yoshida1, Tokutaro Komatsu2

  • 1Division of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto606-8502, Japan.

Inorganic Chemistry
|January 12, 2023
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Summary

This study demonstrates controlling proton-coupled electron transfer (PCET) in platinum complexes via cis-trans isomerization. Geometric changes significantly alter PCET, offering new avenues for catalyst design.

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Area of Science:

  • Coordination Chemistry
  • Catalysis
  • Physical Chemistry

Background:

  • Proton-coupled electron transfer (PCET) is crucial in biochemistry and electrochemistry.
  • Transition-metal complexes are key catalysts for PCET.
  • Controlling PCET often involves tuning metal ions and ligands.

Purpose of the Study:

  • To investigate the impact of metal-ligand isomerization on PCET in platinum complexes.
  • To demonstrate a novel method for controlling PCET through geometric changes.

Main Methods:

  • Synthesis and isolation of cis and trans isomers of Pt(itsq)2.
  • Characterization using single-crystal X-ray diffraction.
  • Computational analysis of electronic structure and protonation effects.

Main Results:

  • The cis and trans isomers of Pt(itsq)2 were successfully isolated and characterized.
  • Cis-to-trans isomerization was induced by immersion in organic solvents.
  • Theoretical calculations revealed significant variations in proton-electron coupling based on geometric configuration.

Conclusions:

  • Metal-ligand isomerization provides a new strategy to control PCET.
  • The geometric configuration of platinum complexes profoundly influences proton-electron coupling.
  • This finding opens possibilities for designing advanced PCET catalysts.