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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...

Ligand Binding Sites

Ligand Binding Sites

Proteins are dynamic macromolecules that carry out a wide variety of essential processes; however, the activities of most proteins depend on their interactions with other molecules or ions, known as ligands.
Protein-ligand interactions are quite specific; even though numerous potential ligands surround a cellular protein at any given time, only a particular ligand can bind to that protein. Moreover, a ligand binds only to a dedicated area on the surface of the protein, known as the...

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...

Predicting Molecular Geometry

Predicting Molecular Geometry

VSEPR Theory for Determination of Electron Pair Geometries

ortho–para-Directing Activators: –CH3, –OH, –&NoBreak;NH2, –OCH3

ortho–para-Directing Activators: –CH₃, –OH, –⁠NH₂, –OCH₃

All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...

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Related Experiment Video

Updated: Aug 29, 2025

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

Thiocarbonylphosphorane and arsorane ligands.

Liam K Burt¹, Anthony F Hill¹, Stephanie L Jones¹

¹Research School of Chemistry, Australian National University, Canberra, Australian Capital Territory, ACT 2601, Australia. a.hill@anu.edu.au.

Chemical Communications (Cambridge, England)

|September 13, 2022

Summary

New tungsten complexes featuring unstable thiocarbonylphosphorane and thiocarbonylarsorane ligands were synthesized. These findings advance the understanding of organometallic chemistry and ligand design for novel catalytic applications.

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Area of Science:

Organometallic Chemistry
Coordination Chemistry
Inorganic Chemistry

Background:

Tungsten complexes are crucial in catalysis.
Thiocarbonyl compounds exhibit unique reactivity.
Stabilizing reactive ligands is a key challenge in coordination chemistry.

Purpose of the Study:

To synthesize and characterize novel tungsten complexes with thiocarbonylphosphorane and thiocarbonylarsorane ligands.
To investigate the stability and reactivity of these unusual ligands.
To explore the utility of these complexes in synthetic chemistry.

Main Methods:

Reaction of phosphonio- or arsoniocarbynes with sulfur.
Isolation and characterization of resulting tungsten complexes using spectroscopic techniques (NMR, IR, Mass Spectrometry).
X-ray crystallography to determine the molecular structure of the synthesized salts.

Main Results:

Successful synthesis of tungsten complexes containing independently unstable thiocarbonylphosphorane and thiocarbonylarsorane ligands.
Characterization of the ligand structure within the [W(η²-C,S-SCAR₃)(CO)₂(Tp*)]PF₆ salt framework.
Demonstration of the formation of these ligands from carbynes and sulfur.

Conclusions:

Thiocarbonylphosphorane and thiocarbonylarsorane ligands can be stabilized within tungsten complexes.
The synthetic route provides access to novel organometallic compounds with potential applications.
This work expands the scope of known ligand types in coordination chemistry.