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Related Concept Videos

Valence Bond Theory02:42

Valence Bond Theory

8.9K
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...
8.9K
Crystal Field Theory - Tetrahedral and Square Planar Complexes02:46

Crystal Field Theory - Tetrahedral and Square Planar Complexes

43.2K
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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Coordination Number and Geometry02:57

Coordination Number and Geometry

16.2K
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.
16.2K
Structural Isomerism02:34

Structural Isomerism

19.5K
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...
19.5K
Colors and Magnetism03:02

Colors and Magnetism

12.0K
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...
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Updated: Jul 27, 2025

Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
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Photogenerated Ni(I)-Bipyridine Halide Complexes: Structure-Function Relationships for Competitive C(sp

David A Cagan1, Daniel Bím1, Brendon J McNicholas1

  • 1Division of Chemistry and Chemical Engineering, Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena, California 91125, United States.

Inorganic Chemistry
|June 6, 2023
PubMed
Summary

Researchers developed new nickel(I)-bipyridine halide complexes for photochemical reactions. Ligand substituents tune reactivity, enabling activation of challenging C(sp2)-Cl bonds via an SNAr mechanism, offering new photocatalytic possibilities.

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[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
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Area of Science:

  • Organometallic Chemistry
  • Photocatalysis
  • Synthetic Methodology

Background:

  • Nickel complexes are crucial catalysts in organic synthesis.
  • Understanding ligand effects on nickel reactivity is key for catalyst design.
  • Activation of strong C-X bonds remains a significant challenge in catalysis.

Purpose of the Study:

  • To photochemically generate and characterize a library of Ni(I)-bipyridine halide complexes.
  • To investigate the structure-reactivity relationships governing oxidative addition and dimerization.
  • To elucidate the mechanism of C(sp2)-Cl bond activation and the role of ligand substituents.

Main Methods:

  • Photochemical synthesis of Ni(I)-bpy halide complexes.
  • Reactivity benchmarking via competitive oxidative addition and dimerization assays.
  • Dual Hammett and computational analysis to probe reaction mechanisms.
  • Investigation of ligand substituent effects on electronic properties (Zeff).

Main Results:

  • A library of Ni(I)(Rbpy)X complexes was successfully synthesized.
  • Ligand substituents strongly influence reactivity, controlling oxidative addition vs. dimerization.
  • C(sp2)-Cl bond activation proceeds via an SNAr-type mechanism, distinct from C(sp2)-Br/I activation.
  • Substituent effects on effective nuclear charge (Zeff) modulate Ni(I) 3d orbital energies and reactivity.

Conclusions:

  • Ligand design is a powerful tool to tune Ni(I) complex reactivity.
  • Modulating Zeff provides a strategy to activate challenging C-X bonds.
  • This work offers new avenues for developing efficient Ni-mediated photocatalytic cycles.