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Valence Bond Theory

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...

Coordination Number and Geometry

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.

Metal-Ligand Bonds

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 Complexes

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...

Crystal Field Theory - Tetrahedral and Square Planar Complexes

Crystal Field Theory - Tetrahedral and Square Planar Complexes

Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...

Structural Isomerism

Structural 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...

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Updated: Jan 6, 2026

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction

Published on: April 10, 2018

Unraveling the coordination structure-performance relationship in Pt₁/Fe₂O₃ single-atom catalyst.

Yujing Ren^1,2, Yan Tang³, Leilei Zhang¹

¹State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 116023, Dalian, China.

Nature Communications

|October 5, 2019

Summary

Researchers developed a new method for single-atom catalysts (SACs) by tuning platinum coordination chemistry on iron oxide. This approach enhances hydrogenation activity to record levels while maintaining selectivity.

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Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction

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Published on: April 10, 2018

Tuning the Acidity of Pt/ CNTs Catalysts for Hydrodeoxygenation of Diphenyl Ether

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Published on: July 18, 2017

Area of Science:

Heterogeneous catalysis
Materials science
Nanotechnology

Background:

Single-atom catalysts (SACs) offer molecular-level structure-performance insights, bridging homogeneous and heterogeneous catalysis.
A key challenge is modifying single-atom coordination without disrupting dispersion.

Purpose of the Study:

To develop an efficient synthetic method for tunable SACs.
To establish a structure-performance relationship for single-atom platinum (Pt) on iron oxide (Fe2O3) supports.
To achieve enhanced catalytic activity and selectivity in hydrogenation reactions.

Main Methods:

A novel synthesis involving ethanediamine chelation of Pt cations followed by rapid thermal treatment (RTT) in an inert atmosphere.
Fine-tuning of Pt single-atom coordination chemistry on Fe2O3 by adjusting RTT temperature.
Characterization of Pt coordination, oxidation state, and catalytic performance in hydrogenation.

Main Results:

Successfully synthesized Pt SACs with tunable coordination chemistry on Fe2O3.
Demonstrated a decrease in Pt-O coordination number with decreasing RTT temperature.
Observed a corresponding decrease in Pt oxidation state and a record-high hydrogenation activity with maintained chemoselectivity.

Conclusions:

The developed RTT method allows precise control over the coordination environment of single atoms.
Tunable coordination chemistry and oxidation states are crucial for optimizing SAC performance.
SACs serve as an effective bridge between homogeneous and heterogeneous catalysis, enabling molecular-level design.