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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...

Stereoisomerism

Stereoisomerism

Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...

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 be...

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...

Complexation Equilibria: The Chelate Effect

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...

Coordination Compounds and Nomenclature

Coordination Compounds and Nomenclature

In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...

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Related Experiment Video

Updated: Jun 13, 2026

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex

Published on: July 27, 2022

Metal-coordination-driven dynamic heteroleptic architectures.

Soumen De¹, Kingsuk Mahata, Michael Schmittel

¹Center of Micro and Nanochemistry and Engineering, Organische Chemie I, Universität Siegen, Adolf-Reichwein-Str., 2, D-57068 Siegen, Germany.

Chemical Society Reviews

|April 27, 2010

Summary

This summary is machine-generated.

Nature utilizes dynamic heteroleptic coordination in biological systems. This review explores principles for assembling dissimilar ligands at metal centers in solution for supramolecular chemistry.

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Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks (MOFs)

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks (MOFs)

Published on: January 17, 2020

Related Experiment Videos

Last Updated: Jun 13, 2026

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex

Published on: July 27, 2022

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks (MOFs)

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks (MOFs)

Published on: January 17, 2020

Area of Science:

Coordination Chemistry
Supramolecular Chemistry
Biomimetic Chemistry

Background:

Dynamic heteroleptic coordination is vital in biological systems (e.g., zinc fingers, hemoglobin) for specific functions.
Biological systems achieve high fidelity through intramolecular coordination using protein backbones as superligands.
Achieving dynamic heteroleptic coordination in solution requires thermodynamic control over freely exchanging ligands.

Purpose of the Study:

To present emerging principles for assembling dissimilar ligands at dynamically exchanging metal centers.
To emphasize the application of these principles in fabricating heteroleptic supramolecular assemblies in solution.
To provide a tutorial review for researchers in coordination and supramolecular chemistry.

Main Methods:

Focuses on thermodynamic control principles for ligand exchange.
Explores the assembly of heteroleptic complexes in solution.
Utilizes concepts from biomimetic coordination chemistry.

Main Results:

Outlines strategies for controlling the assembly of multiple, different ligands around a single metal center.
Demonstrates how thermodynamic control enables dynamic heteroleptic coordination in solution.
Provides a framework for designing novel heteroleptic supramolecular structures.

Conclusions:

Dynamic heteroleptic coordination in solution can be achieved by controlling ligand exchange thermodynamically.
These principles are applicable to the construction of complex heteroleptic supramolecular assemblies.
This work offers insights into mimicking biological coordination strategies in synthetic systems.