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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...

Properties of Transition Metals

Properties of Transition Metals

Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.

Colors and Magnetism

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...

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.

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...

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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Related Experiment Video

Updated: Oct 12, 2025

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV

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Published on: December 29, 2016

A Cobalt Phosphine Complex in Five Oxidation States.

Daniel A Kurtz¹, Jibo Zhang¹, Arvin Sookezian²

¹Rowland Institute at Harvard University, Cambridge, Massachusetts 02142, United States.

Inorganic Chemistry

|November 23, 2021

Summary

This summary is machine-generated.

This study details cobalt complexes in five oxidation states (3+ to 1-) using a unique phosphine ligand (dppv). Structural and electrochemical analyses reveal changes in coordination and geometry across these states.

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Last Updated: Oct 12, 2025

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Area of Science:

Inorganic Chemistry
Coordination Chemistry
Electrochemistry

Background:

Transition metal complexes are crucial in catalysis and materials science.
Understanding the redox behavior of metals like cobalt is key to designing new functional materials.
Cobalt complexes with redox-innocent ligands offer unique opportunities to study electron transfer processes.

Purpose of the Study:

To characterize a series of cobalt complexes across five distinct oxidation states.
To investigate the structural and electronic properties of these complexes.
To demonstrate the utility of the cis-1,2-bis(diphenylphosphino)ethylene (dppv) ligand in stabilizing multiple cobalt oxidation states.

Main Methods:

Electrochemical characterization (cyclic voltammetry) to determine redox potentials.
Spectroscopic techniques for electronic structure analysis.
Single-crystal X-ray diffraction to elucidate molecular structures.

Main Results:

Isolation and characterization of cobalt complexes in the 3+, 2+, 1+, 0, and 1- oxidation states.
Identification of three reversible reductions and one reversible oxidation for the [Co(dppv)2]2+ precursor.
Correlation of oxidation state with changes in coordination number and geometry, from pseudo-octahedral (Co3+) to pseudo-tetrahedral (Co0, Co-).

Conclusions:

The dppv ligand enables the stabilization of an unprecedented five sequential oxidation states in cobalt complexes.
Structural diversity across oxidation states aligns with predictions from crystal-field theory.
This work provides a foundational understanding for designing cobalt-based redox-active materials.