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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 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...

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...

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...

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...

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Updated: Aug 25, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

Published on: April 10, 2015

Cobalt Cyclopentadienyl-Phosphine Dinitrogen Complexes.

Gao-Xiang Wang¹, Xuechao Yan¹, Jianhao Yin¹

¹Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and, Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing, 100871, P. R. China.

Chemistry (Weinheim an Der Bergstrasse, Germany)

|October 19, 2022

Summary

Researchers synthesized novel cobalt-phosphine complexes. These complexes react with white phosphorus (P4) to release nitrogen gas and form unique cobalt-phosphorus structures, advancing coordination chemistry.

Keywords:

P4 activation cobalt dinitrogen activation dinitrogen fixation

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Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus

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Last Updated: Aug 25, 2025

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Published on: April 10, 2015

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

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Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus

Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus

Published on: October 3, 2014

Area of Science:

Coordination Chemistry
Organometallic Chemistry
Phosphorus Chemistry

Background:

Cyclopentadienyl-phosphine ligands are crucial in stabilizing transition metal complexes.
Cobalt complexes are investigated for their reactivity and potential applications in catalysis.
Nitrogen fixation and activation are key areas in inorganic chemistry.

Purpose of the Study:

To synthesize and characterize novel cobalt-phosphine complexes.
To investigate the reactivity of these complexes with molecular nitrogen (N2) and white phosphorus (P4).
To explore the formation of new cobalt-phosphorus frameworks.

Main Methods:

Synthesis of cobalt chlorides (1, LCoIICl) using potassium salts of cyclopentadienyl-phosphine ligands (LK) and CoCl2.
Reduction of cobalt complexes 1 with potassium triethylborohydride (KHBEt3) under N2 atmosphere to form bridging end-on complexes (2a, 2b).
Preparation of 15N2-labeled complex [15N2]-2a via isotopic exchange.
Reaction of complex 2a with P4 molecules and further reduction of complex 2b.
Density Functional Theory (DFT) calculations to support experimental findings.

Main Results:

Successfully synthesized bridging end-on cobalt-nitrogen complexes (LCoI-N2-CoIL, 2a and 2b).
Complex 2a reacted with P4 to release N2 and form a Co-P4-Co moiety (4).
Reduction of complex 2b resulted in P-C bond cleavage and formation of a novel μ-PCy2-bridged Co0-N2 complex (5).
DFT calculations confirmed the structural and reactivity outcomes.

Conclusions:

Novel cobalt-phosphine complexes were synthesized and characterized.
The reactivity of these complexes with P4 demonstrates a pathway for N2 release and formation of cobalt-phosphorus clusters.
The study presents new synthetic routes to unique cobalt-nitrogen and cobalt-phosphorus compounds.