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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...

Carbocations

Carbocations

Carbocations are one of the reaction intermediates formed during several nucleophilic substitutions or elimination reactions. A carbocation is an electron-deficient species with the central carbon atom having six electrons and three bonded atoms. The central carbon in a carbocation is sp2 hybridized with trigonal planar geometry. It has an empty p orbital perpendicular to the plane of the structure that can accept electrons. Thus, carbocations act as strong electrophiles and may react with any...

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...

Complexometric Titration: Ligands

Complexometric Titration: Ligands

Different monodentate and polydentate ligands are used as complexing agents in complexometric titration reactions. The formation of complexes by mono- and bidentate ligands involves two or more intermediate steps, limiting their use as complexing agents. In comparison, polydentate ligands can form complexes with metal ions in a single-step process, facilitating sharper end points. This means polydentate ligands, such as amino carboxylic acid derivatives, are most commonly employed in...

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...

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.

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Using Cyclic Voltammetry, UV-Vis-NIR, and EPR Spectroelectrochemistry to Analyze Organic Compounds

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Tunable carbocation-based redox active ambiphilic ligands: synthesis, coordination and characterization.

Liangyong Mei¹, José M Veleta, Jan Bloch

¹University of Arizona, Department of Chemistry and Biochemistry, Tucson, AZ, USA. tgianetti@email.arizona.edu.

Dalton Transactions (Cambridge, England : 2003)

|March 19, 2020

Summary

Researchers synthesized novel redox-active ambiphilic ligands and studied their coordination with cobalt and nickel halides. These ligands form unique zwitterionic metallate complexes with interesting structural and electronic properties, observed in both solid and solution states.

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Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides

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Published on: September 7, 2019

Area of Science:

Coordination Chemistry
Organometallic Chemistry
Materials Science

Background:

Ambiphilic ligands offer unique coordination modes due to their dual Lewis acid/base character.
First-row late transition metals (Co, Ni) are crucial in catalysis and materials.

Purpose of the Study:

To synthesize and characterize novel redox-active ambiphilic ligands (L1-L3).
To investigate the coordination chemistry of these ligands with cobalt and nickel halides.
To explore the structural, electronic, and solid-state properties of the resulting metal complexes.

Main Methods:

Ligand synthesis and characterization.
Coordination of ligands to metal halides (Co, Ni).
Single crystal X-ray diffraction, cyclic voltammetry, UV-Vis spectroscopy, and DFT calculations.

Main Results:

Novel redox-active ambiphilic ligands L1-L3 were successfully synthesized.
Coordination to Co and Ni halides yielded zwitterionic metallate trichloride complexes.
Characterization revealed tetrahedral geometry and potential intra-complex electrostatic interactions in the solid state.
DFT calculations confirmed the solid-state nature of observed interactions.

Conclusions:

The synthetic tunability of the ligand scaffold allows for control over rigidity and electronic properties.
The formation of zwitterionic metallate complexes demonstrates a novel coordination motif.
The observed solid-state interactions highlight the importance of crystal packing and intermolecular forces in organometallic complexes.