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Related Concept Videos

Complexation Equilibria: The Chelate Effect01:19

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...
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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...
EDTA: Chemistry and Properties01:22

EDTA: Chemistry and Properties

Polydentate ligands are most widely used in complexometric titrations because they form more stable complexes with the metal ions than mono- or bidentate ligands due to the chelate effect. Examples of polydentate ligands are ethylenediaminetetraacetic acid (EDTA), crown ethers, and cryptands. The most important feature of optimal polydentate ligands is the ability to form 1:1 complexes in a single-step process. Amino carboxylic acid derivatives are frequently used as complexing agents. EDTA is...
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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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Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...
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Diels–Alder Reaction: Characteristics of Dienes

The Diels–Alder reaction brings together a diene and a dienophile to form a six-membered ring. Both components have unique characteristics that influence the rate of the reaction.
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable, the...

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Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
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Noninnocence in metal complexes: a dithiolene dawn.

Richard Eisenberg1, Harry B Gray

  • 1Department of Chemistry, University of Rochester, Rochester, New York 14627, USA. eisenberg@chem.rochester.edu

Inorganic Chemistry
|September 15, 2011
PubMed
Summary

Early inorganic chemistry research on metal complexes with dithiolene ligands revealed noninnocent behavior, challenging traditional oxidation-state descriptions. These foundational studies explored unique electronic structures and geometries, paving the way for future investigations.

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Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene

Published on: March 20, 2017

Area of Science:

  • Inorganic Chemistry
  • Coordination Chemistry
  • Materials Science

Background:

  • Noninnocence in inorganic chemistry originates from studies of metal complexes with unsaturated dithiolate ligands.
  • Early research in the 1960s focused on homoleptic bis and tris dithiolene complexes.

Purpose of the Study:

  • Investigate the structural, electrochemical, spectroscopic, and magnetic properties of dithiolene metal complexes.
  • Understand the electronic structures that defied conventional oxidation-state assignments.
  • Explore novel coordination geometries and electron transfer mechanisms.

Main Methods:

  • Synthesis of homoleptic bis and tris dithiolene complexes.
  • Characterization using structural, electrochemical, and spectroscopic techniques.
  • Computational analysis employing extended Hückel and semiempirical methods.

Main Results:

  • Dithiolene complexes exhibited facile one-electron transfers and intense colors.
  • Square-planar and trigonal-prismatic coordination geometries were observed.
  • Extensive ligand-metal orbital mixing indicated redox activity primarily on the ligand.

Conclusions:

  • Early investigations established the noninnocent nature of dithiolene ligands.
  • These foundational studies provided a basis for understanding metal complexes with redox-active ligands.
  • Modern methods confirm and expand upon the initial interpretations of these systems.