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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.

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,...

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...

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...

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...

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...

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Related Experiment Video

Updated: Apr 17, 2026

Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates

Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates

Published on: February 15, 2016

U(III)-CN versus U(IV)-NC coordination in tris(silylamide) complexes.

Alexandre Hervé¹, Yamina Bouzidi, Jean-Claude Berthet

¹CEA, IRAMIS, UMR 3685 NIMBE, CEA/CNRS NIMBE, CEA/Saclay , 91191 Gif-sur-Yvette, France.

Inorganic Chemistry

|February 17, 2015

Summary

Uranium complexes were synthesized and characterized, revealing distinct coordination modes for cyanide ligands in U(III) versus U(IV) states. Density functional theory calculations explained these preferences based on electronic structures and bonding energies.

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Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents

Published on: May 28, 2014

Area of Science:

Organometallic Chemistry
Uranium Chemistry
Coordination Chemistry

Background:

Uranium complexes with bulky silylamide ligands are of interest for fundamental studies.
Understanding metal-ligand bonding in uranium complexes is crucial for predicting reactivity.
Previous studies on U(III) cyanide complexes showed C-atom coordination.

Purpose of the Study:

To synthesize and characterize novel uranium complexes with bulky silylamide ligands.
To investigate the coordination behavior of cyanide ligands with uranium.
To differentiate between U(III) and U(IV) coordination modes using experimental and computational methods.

Main Methods:

Synthesis of cationic, neutral, and dinuclear uranium complexes.
Characterization using X-ray crystallography.
Density functional theory (DFT) calculations for electronic structure analysis and bonding energy comparisons.

Main Results:

Synthesis of various uranium complexes, including cationic [UN*3][BPh4] and neutral [UN*3X] species.
Formation of cyanido-bridged dinuclear and mononuclear uranium complexes.
Observation of U-NC isocyanide coordination in U(IV) complexes, contrasting with U(III) U-CN coordination.

Conclusions:

The coordination mode of cyanide ligands (U-CN vs. U-NC) is dependent on the uranium oxidation state.
DFT calculations successfully explain the observed coordination preferences based on electronic structures and metal-ligand bonding.
A balance of covalent, ionic, and steric factors governs the uranium-cyanide/isocyanide bonding.