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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: Factors Influencing Stability of Complexes01:09

Complexation Equilibria: Factors Influencing Stability of Complexes

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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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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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Stereoisomerism02:52

Stereoisomerism

12.1K
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...
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Complexometric Titration: Ligands00:43

Complexometric Titration: Ligands

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Different monodentate and polydentate ligands are used as complexing agents in complexometric titration reactions. The formation of complexes by mono- and bidentate ligands involves two or more intermediate steps, limiting their use as complexing agents. In comparison, polydentate ligands can form complexes with metal ions in a single-step process, facilitating sharper end points. This means polydentate ligands, such as amino carboxylic acid derivatives, are most commonly employed in...
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EDTA: Auxiliary Complexing Reagents01:26

EDTA: Auxiliary Complexing Reagents

616
EDTA titrations are usually carried out in highly basic conditions, where the fully deprotonated form of EDTA, Y4−, actively complexes with the free metal ions in the solution. Several metal ions precipitate as hydrous oxide (hydroxides, oxides, or oxyhydroxides) under these conditions, lowering the concentration of free metal ions in the solution. For this reason, auxiliary complexing agents or ligands such as ammonia, tartrate, citrate, or triethanolamine are used in EDTA titrations to...
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Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides
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Optically active bis(aminophenols) and their metal complexes.

Halen Carbonel1, Timothy D Mikulski1, Kahargyan Nugraha1

  • 1Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556-5670, USA. Seth.N.Brown.114@nd.edu.

Dalton Transactions (Cambridge, England : 2003)
|September 5, 2023
PubMed
Summary
This summary is machine-generated.

Optically active chiral ligands were synthesized and used to create novel palladium, platinum, and osmium complexes. These complexes exhibit unique structural and electronic properties, confirmed by spectroscopic and computational analyses.

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Area of Science:

  • Coordination Chemistry
  • Organometallic Chemistry
  • Chiral Ligand Synthesis

Background:

  • Development of optically active ligands is crucial for asymmetric catalysis and materials science.
  • Bis(aminophenol) ligands offer versatile coordination environments for metal complexes.
  • Understanding the stereochemistry of metal complexes is key to predicting their properties.

Purpose of the Study:

  • To synthesize novel optically active bis(aminophenol) ligands: (R)-2,2'-diaminobinaphthyl (BiniqH4) and (R,R)-2,3-butanediyldianthranilate (BdanH4).
  • To prepare and characterize Group 10 metal complexes (Pd, Pt) and Osmium oxo complexes using these chiral ligands.
  • To investigate the structural, stereochemical, and electronic properties of the resulting metal complexes.

Main Methods:

  • Ligand synthesis via condensation reactions.
  • Oxidative metalation to form bis(iminosemiquinone)metal complexes.
  • Spectroscopic techniques (circular dichroism, optical spectra) and TDDFT calculations for electronic structure analysis.

Main Results:

  • Successful synthesis of chiral bis(aminophenol) ligands and their corresponding Pd, Pt, and Os complexes.
  • Demonstration of distinct coordination modes and stereochemistry based on ligand structure (e.g., C2 axis orientation).
  • Correlation of electronic structures with observed circular dichroism spectra, supported by theoretical calculations.

Conclusions:

  • The synthesized chiral ligands enable the formation of structurally diverse and stereochemically defined metal complexes.
  • The study provides insights into the relationship between ligand chirality, metal coordination, and complex electronic properties.
  • These findings contribute to the design of new chiral organometallic compounds for potential applications.