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Related Concept Videos

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.
Formation of Complex Ions03:45

Formation of Complex Ions

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...
Coordination Number and Geometry02:57

Coordination Number and Geometry

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.
Ionic Crystal Structures02:42

Ionic Crystal Structures

Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
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...
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...

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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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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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An anionic, tetragonal copper(II) superoxide complex.

Patrick J Donoghue1, Aalo K Gupta, David W Boyce

  • 1Department of Chemistry, Supercomputing Institute, and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, USA.

Journal of the American Chemical Society
|October 28, 2010
PubMed
Summary
This summary is machine-generated.

Researchers identified a novel copper(II)-superoxide complex. This complex, featuring a hindered pyridinedicarboxamide ligand, exhibits unique basic properties in reactions, offering new insights into oxidation catalysis intermediates.

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[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
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[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

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Area of Science:

  • Bioinorganic Chemistry
  • Coordination Chemistry
  • Catalysis

Background:

  • Copper-oxygen species are crucial intermediates in various oxidation catalysis reactions.
  • Understanding the structure and reactivity of these intermediates is key to designing efficient catalysts.
  • Previous studies have explored copper-superoxide complexes, but their precise roles and behaviors remain areas of active investigation.

Purpose of the Study:

  • To identify and characterize a novel copper(II)-superoxide complex.
  • To elucidate the structural and electronic properties of this complex.
  • To investigate its reactivity, particularly in comparison to known copper-superoxide species.

Main Methods:

  • Synthesis of a copper(II)-superoxide complex supported by a sterically hindered pyridinedicarboxamide ligand.
  • Spectroscopic characterization using UV-vis, NMR, EPR, and resonance Raman spectroscopy.
  • Density Functional Theory (DFT) calculations to propose the complex's structure.
  • Reactivity studies involving reaction with a copper(I) precursor and phenols.

Main Results:

  • Identification of a stable Cu(II)-superoxide complex with a proposed tetragonal, end-on superoxide structure.
  • Spectroscopic data (UV-vis, NMR, EPR, resonance Raman) and DFT calculations support the proposed structure.
  • The complex reacts with [(tmpa)Cu(CH3CN)]OTf to form a trans-1,2-peroxodicopper(II) species.
  • In reactions with phenols, the complex functions as a base, unlike other known Cu(II)-superoxide complexes that act as electrophiles.

Conclusions:

  • A novel Cu(II)-superoxide complex has been successfully synthesized and characterized.
  • The findings provide valuable insight into the nature of copper-oxygen intermediates in oxidation catalysis.
  • The unique basic reactivity of this complex opens new avenues for catalytic applications and mechanistic studies.