Related Experiment Video
Updated: May 24, 2026
![[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
09:12
[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Dioxygen reactivity of new bispidine-copper complexes
Peter Comba1, Christina Haaf, Stefan Helmle
1Anorganisch-Chemisches Institut, Universität Heidelberg, INF 270, D-69120 Heidelberg, Germany. peter.comba@aci.uni-heidelberg.de
Inorganic Chemistry
|February 16, 2012
Summary
Copper complexes with bispidine ligands show diverse reactivity with dioxygen, forming various species like superoxo and peroxo complexes. Ligand structure and conditions control which copper-dioxygen adducts form.
Area of Science:
- Coordination Chemistry
- Bioinorganic Chemistry
- Organometallic Chemistry
Background:
- Copper complexes are vital in biological systems for oxygen activation.
- Bispidine ligands offer tunable coordination environments for metal ions.
- Understanding copper-oxygen interactions is key to catalysis and bioinorganic modeling.
Purpose of the Study:
- To investigate the reactivity of copper complexes with novel bispidine ligands towards dioxygen.
- To characterize the different dioxygen adducts formed and their structural diversity.
- To elucidate the influence of ligand structure and reaction conditions on copper-dioxygen speciation.
Main Methods:
- Synthesis and characterization of copper complexes with three second-generation bispidine ligands.
- Spectroscopic studies including UV-vis, ESI-MS, EPR, and resonance Raman spectroscopy.
- Computational analysis using density functional theory (DFT) to understand reaction mechanisms.
Main Results:
- Formation of various copper-dioxygen species including mono- and dinuclear superoxo, peroxo, and hydroperoxo complexes.
- Demonstration of facile interconversion between different adducts by altering ligand structure or experimental conditions.
- Characterization of specific end-on peroxodicopper(II) and mononuclear hydroperoxocopper(II) complexes.
- Observation of reversible dioxygen binding leading to a metastable superoxocopper(II) complex with one ligand.
Conclusions:
- Copper-bispidine complexes exhibit rich and tunable reactivity with dioxygen.
- Ligand design and reaction conditions are critical for controlling the outcome of copper-oxygen interactions.
- DFT analysis provides insights into the mechanisms governing dioxygen binding and adduct formation.
More Related Videos
Related Concept Videos
03:02Colors 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.
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.
02:34Structural Isomerism
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 be...
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 be...
02:42Valence 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...
01:11ortho–para-Directing Activators: –CH3, –OH, –NH2, –OCH3
All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...
02:51Metal-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...
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...
01:29Diels–Alder Reaction: Characteristics of Dienes
The Diels–Alder reaction brings together a diene and a dienophile to form a six-membered ring. Both components have unique characteristics that influence the rate of the reaction.
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable, the...
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable, the...