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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...

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...

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...

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.
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Complexation Equilibria: The Chelate Effect

Complexation Equilibria: The Chelate Effect

In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...

Complexation Equilibria: Factors Influencing Stability of Complexes

Complexation Equilibria: Factors Influencing Stability of Complexes

In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...

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Synthesis of Information-bearing Peptoids and their Sequence-directed Dynamic Covalent Self-assembly

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Published on: February 6, 2020

Polyanionic Imido-P(V) Ligands: From Transition Metal Complexes to Coordination Driven Self-Assemblies.

Meghamala Sarkar¹, Prabhakaran Rajasekar¹, Cavya Jose¹

¹Department of Chemistry, Indian Institute of Science Education and Research, Pune, Dr. Homi Bhabha Road, Pune, 411008, India.

Chemical Record (New York, N.Y.)

|December 28, 2021

Summary

This study explores imido-P(V) anions, coordinating them with soft transition metals like silver (Ag(I)) and palladium (Pd(II)) to form novel clusters and cages. These structures exhibit unique host-guest chemistry and are used for chiral recognition and separation.

Keywords:

Cage molecules Host-Guest Chemistry P−N ligands cluster compounds imido anions

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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
Supramolecular Chemistry
Main Group Chemistry

Background:

Imido-anions of main group elements, isoelectronic to oxo groups, have been studied for decades.
Polyimido-P(V) anions resemble phosphorus oxo moieties but their coordination chemistry is limited to strong organometallic reagents and anhydrous conditions.
Previous methods restricted the coordination chemistry of imido-P(V) anions to main group metal ions.

Purpose of the Study:

To explore the coordination chemistry of imido-P(V) anions with soft transition metals, specifically Ag(I) and Pd(II).
To synthesize self-assembled clusters and cages using these imido-P(V) anions.
To investigate the host-guest chemistry and potential applications of the resulting supramolecular structures.

Main Methods:

Reaction of Ag(I) salts with 2-pyridyl functionalized phosphonium salts and phosphoric triamides to form Ag(I) clusters.
One-pot reaction of Pd(II) salts with imido-phosphate trianions to generate Pd(II) clusters and cages.
Synthesis of chiral imido-phosphate trianions for enantiopure cage construction.

Main Results:

Isolation of mono- and dianionic imido ligands and formation of tri-, penta-, hepta-, and octanuclear Ag(I) clusters.
Generation of elusive imido-phosphate trianions and their assembly into tri- and hexanuclear Pd(II) clusters.
Construction of neutral tetrahedral and cubic cages using Pd(II) clusters and imido-phosphate trianions as building blocks.
Synthesis of enantiopure chiral cages for chiral recognition and enantio-separation.
Observation of polyradical framework structures in some chiral cages.

Conclusions:

Soft transition metals like Ag(I) and Pd(II) enable novel coordination chemistry with imido-P(V) anions.
Self-assembled clusters and cages with unique architectures and host-guest properties were successfully synthesized.
Chiral cages demonstrate potential for asymmetric catalysis and separation of chiral molecules.