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Related Concept Videos

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 - 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...
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.
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...
Complexometric Titration: Ligands00:43

Complexometric Titration: Ligands

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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Fast O2 binding at dicopper complexes containing Schiff-base dinucleating ligands.

Anna Company1, Laura Gómez, Rubén Mas-Ballesté

  • 1Departament de Química and Institut de Química Computacional, Universitat de Girona, Campus de Montilivi E-17071, Girona, Spain.

Inorganic Chemistry
|May 16, 2007
PubMed
Summary

New dicopper(I) complexes mimic type 3 copper proteins, showing rapid O2 binding and activation. These complexes, featuring Schiff-base ligands, demonstrate a synergistic role of copper ions in oxygen chemistry.

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Structure and Coordination Determination of Peptide-metal Complexes Using 1D and 2D 1H NMR
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Published on: December 16, 2013

Area of Science:

  • Coordination Chemistry
  • Bioinorganic Chemistry
  • Organometallic Chemistry

Background:

  • Type 3 copper proteins play crucial roles in biological oxygen processing.
  • Developing synthetic models is key to understanding their structure-function relationships.
  • Dicopper(I) complexes with specific ligand environments are designed to mimic these active sites.

Purpose of the Study:

  • To synthesize and characterize a new family of dicopper(I) complexes with Schiff-base ligands.
  • To investigate the reaction of these complexes with molecular oxygen (O2).
  • To elucidate the structural and mechanistic aspects of O2 binding and activation, aiming to replicate features of type 3 copper proteins.

Main Methods:

  • Synthesis and characterization of dicopper(I) complexes using Schiff-base ligands.
  • Single-crystal X-ray diffraction for solid-state structure determination.
  • 1H and 19F NMR spectroscopy for solution studies and dynamic process identification.
  • UV-vis spectroscopy and resonance Raman analysis for characterizing O2 adducts.
  • DFT calculations to study O2 adducts and isomer stability.
  • Stopped-flow UV-vis spectroscopy to determine reaction kinetics.

Main Results:

  • A new family of dicopper(I) complexes, [CuI2RL](X)2, was successfully prepared and characterized.
  • Solid-state structures revealed both polymeric and monomeric forms depending on the ligand and counterion.
  • Complexes in acetone rapidly react with O2 to form metastable [CuIII2(mu-O)2] species.
  • Intermolecular O2 binding was observed in dichloromethane.
  • DFT studies supported the CuIII2(mu-O)2 structure over the CuII2(mu-eta2:eta2-O2) isomer.
  • An unexpectedly fast O2 reaction rate (k=3.82(4)x10^3 M^-1 s^-1) was measured for specific complexes.

Conclusions:

  • The synthesized dicopper(I) complexes effectively model structural aspects of type 3 copper proteins.
  • A synergistic role of the copper ions in O2 binding and activation was clearly established.
  • The complexes exhibit rapid O2 reactivity, forming stable Cu(III)-oxo species.
  • While mimicking O2 processing, these models did not lead to aromatic hydroxylation under tested conditions.