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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...

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...

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...

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...

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Structure and Coordination Determination of Peptide-metal Complexes Using 1D and 2D 1H NMR

Structure and Coordination Determination of Peptide-metal Complexes Using 1D and 2D 1H NMR

Published on: December 16, 2013

Hepta-coordinated Ni(II) assemblies - structure and magnetic studies.

Mateusz Reczyński¹, Mitsuru Akaki², Takamitsu Fukuda³

¹Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Kraków, Poland. beata.nowicka@uj.edu.pl.

Dalton Transactions (Cambridge, England : 2003)

|April 21, 2021

Summary

This study synthesizes novel nickel complexes with unique coordination geometries. Magnetic studies reveal significant magnetic anisotropy in these nickel(II) compounds, explained by advanced computational methods.

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Area of Science:

Coordination Chemistry
Magnetochemistry
Computational Chemistry

Background:

Nickel(II) complexes are crucial in various chemical applications.
Understanding magnetic properties of metal ions requires detailed structural analysis.
Pentagonal bipyramid geometry influences magnetic behavior.

Purpose of the Study:

Synthesize and characterize novel mononuclear and bimetallic nickel complexes.
Investigate the structural and magnetic properties of these compounds.
Correlate magnetic anisotropy with electronic structure using computational methods.

Main Methods:

Synthesis of mononuclear and bimetallic nickel complexes.
X-ray crystallography for structural determination.
High-field Electron Paramagnetic Resonance (EPR) and magnetometry.
Ab initio CASSCF/NEVPT2 calculations.

Main Results:

Three nickel compounds, including mononuclear and a trinuclear bimetallic structure, were synthesized.
All compounds feature Ni(II) in a pentagonal bipyramid coordination.
Magnetic studies revealed large Ni(II) anisotropy (D values: -10.5 to -21.2 cm-1) with minimal magnetic interactions.
Computational methods successfully reproduced the observed easy-axis magnetic anisotropies.

Conclusions:

The synthesized nickel complexes exhibit significant magnetic anisotropy.
The pentagonal bipyramid geometry and ligand field are key factors in the observed magnetic properties.
Computational modeling provides accurate insights into the magnetic behavior of these systems.