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Extraction: Advanced Methods00:56

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Metal ions can be separated from one another by complexation with organic ligands–the chelating agent– to form uncharged chelates. Here, the chelating agent must contain hydrophobic groups and behave as a weak acid, losing a proton to bind with the metal. Since most organic ligands used in this process are insoluble or undergo oxidation in the aqueous phase, the chelating agent is initially added to the organic phase and extracted into the aqueous phase. The metal-ligand complex is...
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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...
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Complexation Equilibria: The Chelate Effect01:19

Complexation Equilibria: The Chelate Effect

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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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Acid Halides to Ketones: Gilman Reagent01:14

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3.0K
Lithium dialkyl cuprate, also known as Gilman reagents, selectively reduces acid halides to ketones. The acid chloride is treated with Gilman reagent at −78 °C in the presence of ether solution to produce a ketone in good yield.
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Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
5.0K
Formation of Complex Ions03:45

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A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
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Chalcogen bonding in copper(II)-mediated synthesis.

Vusala A Aliyeva1, Atash V Gurbanov1,2, Abdallah G Mahmoud1,3

  • 1Centro de Química Estrutural, Institute of Molecular Sciences, Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal. organik10@hotmail.com.

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Summary

Chalcogen bonds (ChB) are crucial noncovalent interactions. This study demonstrates their role in metal complex activation and solid-state structure, enhanced by metal coordination.

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Area of Science:

  • Supramolecular Chemistry
  • Inorganic Chemistry
  • Computational Chemistry

Background:

  • Chalcogen bonds (ChB) are noncovalent interactions involving electrophilic chalcogen atoms.
  • ChBs exhibit comparable strength and directionality to hydrogen and halogen bonds.
  • Divalent/tetravalent chalcogen atoms offer multiple electrophilic centers, enhancing binding opportunities.

Purpose of the Study:

  • To demonstrate the role of ChB in the secondary coordination sphere of metal complexes.
  • To investigate copper(II)-mediated activation of dioxygen or nitrile groups via ChB.
  • To analyze the structure-directing role and strength of ChBs in solid-state architectures.

Main Methods:

  • Density Functional Theory (DFT) calculations to evaluate ChB strength.
  • Analysis of molecular electrostatic potential (MEP) surfaces.
  • Investigation of metal-coordination effects on ChB interactions.

Main Results:

  • ChB plays a significant structure-directing role in solid-state architectures of metal complexes.
  • Copper(II)-mediated activation of dioxygen/nitrile groups was observed through ChB.
  • Metal coordination enhances the ability of selenoxide derivatives to form strong ChBs.

Conclusions:

  • Chalcogen bonds are vital in the secondary coordination sphere of metal complexes.
  • Metal coordination strengthens ChBs by modifying the electronic properties of the chalcogen atom.
  • This work highlights the synthetic utility and structural importance of ChB in coordination chemistry.