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A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
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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...
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Isomerism in Complexes
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Highly Distorted Bismuth-Nickel(II) Complex.

Alexander C Brannan1, Dagyum Yoo1, Jonghoon Choi1

  • 1Department of Chemistry, Seoul National University, Seoul 08826, Republic of Korea.

Inorganic Chemistry
|May 23, 2023
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Summary
This summary is machine-generated.

This study introduces novel nickel complexes with bismuth-containing pincer ligands, revealing unique bismuth-nickel bonding and structural influences. These findings pave the way for new heterobimetallic catalysts in chemical transformations.

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Area of Science:

  • Organometallic Chemistry
  • Coordination Chemistry
  • Materials Science

Background:

  • Nickel complexes are crucial in catalysis, but incorporating heavier p-block elements like bismuth offers new possibilities.
  • Pincer ligands provide robust coordination environments for metal centers, influencing reactivity and stability.
  • Understanding heterobimetallic interactions is key to designing advanced catalytic systems.

Purpose of the Study:

  • To synthesize and characterize novel nickel complexes featuring bismuth-containing pincer ligands.
  • To investigate the structural and electronic influence of bismuth on a nickel(II) center.
  • To explore the potential of bismuth-nickel moieties in catalysis and chemical transformations.

Main Methods:

  • Synthesis of bismuth-containing pincer ligands (BiP3) and their subsequent reaction with Ni(0).
  • Characterization using X-ray crystallography, spectroscopy, and elemental analysis.
  • Investigation of reactivity through ligand modification, methylation, and migratory insertion reactions (e.g., with CO).

Main Results:

  • Successful synthesis of a 4-coordinate Bi-Ni(II) complex and a 5-coordinate nickel(II) complex with a methylated bismuth site.
  • X-ray crystallography revealed significant structural distortions and elongated Bi-Ni bonds upon methylation, indicating altered bonding interactions.
  • Bismuth incorporation led to a Ni(I)-Bi(II) character and influenced the geometry of nickel(II) pincer complexes, distinct from previously reported analogues.
  • Migratory insertion of CO into the Ni-C bond demonstrated the potential for catalytic transformations and influenced reaction kinetics.

Conclusions:

  • Bismuth-containing pincer ligands can significantly influence the structure and bonding of nickel complexes.
  • The bismuth-nickel moiety exhibits unique electronic properties and cooperativity, suggesting potential as a novel heterobimetallic catalytic site.
  • These findings open new avenues for designing advanced bimetallic complexes for diverse chemical applications.