Related Experiment Video
Updated: Aug 14, 2025
16:11
Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
Published on: June 8, 2022
2.4K
Two-Electron Mixed Valency in a Heterotrimetallic Nickel-Vanadium-Nickel Complex
Michael K Wojnar1, Joseph W Ziller1, Alan F Heyduk1
1Department of Chemistry, University of California at Irvine, Irvine, California92677-2025, United States.
Inorganic Chemistry
|January 12, 2023
Summary
This study explores mixed-valence complexes for electron transfer, detailing the synthesis and characterization of a novel heterotrimetallic vanadium-nickel cluster. The findings highlight metal-metal interactions and flexible coordination in reversible electron transfer.
Area of Science:
- Coordination Chemistry
- Inorganic Chemistry
- Electron Transfer Studies
Background:
- Mixed-valence complexes are key for studying electron transfer within molecular frameworks.
- Understanding electron localization and transfer is crucial for designing functional molecular materials.
Purpose of the Study:
- To synthesize and characterize a novel heterotrimetallic mixed-valence complex, [V(SNS)2{Ni(dppe)}2]-.
- To investigate the electronic structure and electron transfer properties of the synthesized complex and its oxidized form.
- To elucidate the role of metal-metal interactions and coordination geometry in enabling reversible electron transfer.
Main Methods:
- Synthesis of the diamagnetic heterotrimetallic anion [V(SNS)2{Ni(dppe)}2]- via reduction of (dppe)NiCl2.
- One-electron oxidation to yield the neutral, paramagnetic V(SNS)2{Ni(dppe)}2.
- Solid-state structural analysis, continuous-wave X-band electron paramagnetic resonance (EPR) spectroscopy, electrochemical investigations, and density functional theory (DFT) computations.
Main Results:
- The structure of the neutral complex revealed distinct coordination environments for the two nickel ions, with one exhibiting a short Ni-V distance indicative of a metal-metal bond.
- EPR spectroscopy, electrochemistry, and DFT calculations confirmed that the unpaired electron in the neutral complex is localized on the bridging [V(SNS)2] metalloligand.
- The complex is best described as a two-electron mixed-valence system, showcasing reversible electron transfer capabilities.
Conclusions:
- The study successfully synthesized and characterized a novel mixed-valence vanadium-nickel cluster.
- Metal-metal interactions and adaptable coordination geometries are critical for facilitating multiple, reversible electron transfer processes in small cluster complexes.
- This work provides insights into the fundamental principles governing electron transfer in molecular systems.
More Related Videos
10:57Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction
Published on: April 10, 2018
18.3K
11:04Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides
Published on: September 7, 2019
9.3K
Related Concept Videos
02:42Valence Bond Theory
9.0K
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...
9.0K
02:57Coordination Number and Geometry
16.4K
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.
16.4K
02:51Metal-Ligand Bonds
21.3K
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...
21.3K
01:19Complexation Equilibria: The Chelate Effect
590
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...
590
02:34Structural Isomerism
19.6K
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...
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...
19.6K
03:02Colors and Magnetism
12.2K
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...
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...
12.2K