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Related Concept Videos

Metal-Ligand Bonds02:51

Metal-Ligand Bonds

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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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Alkyl Halides02:45

Alkyl Halides

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Structural Properties
Alkyl halides are halogen-substituted alkanes wherein one or more hydrogen atoms of an alkane is replaced by a halogen atom such as fluorine, chlorine, bromine, or iodine. The carbon atom in an alkyl halide is bonded to the halogen atom, which is sp3-hybridized and exhibits a tetrahedral shape.
Unlike alkyl halides, compounds in which a halogen atom is bonded to an sp2 -hybridized carbon atom of a carbon-carbon double bond (C=C) are called vinyl halides. Whereas aryl...
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Properties of Organometallic Compounds01:23

Properties of Organometallic Compounds

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Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
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ortho–para-Directing Deactivators: Halogens01:24

ortho–para-Directing Deactivators: Halogens

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Halogens are ortho–para directors. They are more electronegative than carbon. Therefore, as ring substituents, they can withdraw electrons through the inductive effect and deactivate the aromatic ring towards electrophilic substitution. Halogens also have an electron-donating resonance effect on the ring, which influences the orientation of the incoming electrophile. If an electrophile attacks at the ortho or the para position, the halogen donates electrons and stabilizes the intermediate...
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Base-Promoted α-Halogenation of Aldehydes and Ketones00:51

Base-Promoted α-Halogenation of Aldehydes and Ketones

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α-Halogenation of aldehydes and ketones is a reaction involving the substitution of α hydrogens with halogens in the presence of a base.  The reaction begins with the abstraction of  α hydrogen by the base to produce a nucleophilic enolate ion. This intermediate undergoes a subsequent nucleophilic substitution with the halogen to produce a monohalogenated carbonyl compound. If the starting substrate has more than one α hydrogen, it is difficult to stop the reaction...
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Complexation Equilibria: Factors Influencing Stability of Complexes01:09

Complexation Equilibria: Factors Influencing Stability of Complexes

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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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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding
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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding

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Designer Metallic Acceptor-Containing Halogen Bonds: General Strategies.

Xinxing Zhang1, Kit Bowen1

  • 1Departments of Chemistry and Material Sciences, Johns Hopkins University, Baltimore, Maryland, MD, 21218, USA.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|March 16, 2017
PubMed
Summary

Researchers propose two strategies for designing metallic anions capable of halogen bonding (XB). This opens new avenues for XB applications, previously limited to non-metallic acceptors.

Keywords:
aluminiumbond theoryhalogen bondingmetal hydridessuperatoms

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Area of Science:

  • Computational Chemistry
  • Supramolecular Chemistry
  • Materials Science

Background:

  • Hydrogen bonding (HB) and halogen bonding (XB) are electrostatic interactions with analogous applications.
  • While metal anions are effective HB acceptors, their use in XB has been unexplored due to reactivity.
  • This limits the scope of XB theory and applications.

Purpose of the Study:

  • To propose novel strategies for designing metallic anions as effective XB acceptors.
  • To overcome the reactivity limitations of metal anions in XB interactions.
  • To expand the theoretical understanding and practical applications of halogen bonding.

Main Methods:

  • Utilizing ab initio calculations to investigate potential metallic XB acceptor designs.
  • Strategy 1: Employing metal cluster anions with high electron detachment energy (e.g., Al13-).
  • Strategy 2: Designing ligand-passivated metal cores to stabilize negative charges (e.g., PtH5-, PtZnH5-, PtMgH5-).

Main Results:

  • Two viable strategies for creating metallic XB acceptors were computationally explored.
  • The proposed metallic anions demonstrate potential for stable halogen bonding interactions.
  • Theoretical evidence supports the feasibility of using specific metal clusters and passivated cores.

Conclusions:

  • The study presents a breakthrough in designing metallic XB acceptors, addressing a gap in XB theory.
  • The proposed strategies are expected to facilitate the discovery of new metallic acceptor-containing XBs.
  • This research broadens the scope of supramolecular chemistry and materials design.