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Related Concept Videos

Radical Formation: Homolysis00:54

Radical Formation: Homolysis

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A bond is formed between two atoms by sharing two electrons. When this bond is broken by supplying sufficient energy, either two electrons can be taken up by one atom forming ions by the cleavage called heterolysis, or the two electrons are shared by two atoms, with one each creating radicals by the cleavage called homolysis.
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Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration02:34

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The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.
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Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride01:26

Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride

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Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
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Radical Formation: Abstraction00:47

Radical Formation: Abstraction

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The electron of an atom can be abstracted from a compound by a relatively unstable radical to generate a new radical of relatively greater stability. For example, an initiator which forms radicals by homolysis can abstract a suitable species like a hydrogen atom or a halogen atom from a compound to generate a new radical. This ability of radicals to propagate by abstraction is a crucial feature of radical chain reactions.
Even though homolysis produces radicals, it is different from radical...
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Radical Reactivity: Overview01:11

Radical Reactivity: Overview

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Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
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IR Spectrum Peak Splitting: Symmetric vs Asymmetric Vibrations01:08

IR Spectrum Peak Splitting: Symmetric vs Asymmetric Vibrations

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Identical bonds within a polyatomic group can stretch symmetrically (in-phase) or asymmetrically (out-of-phase). Similar to hydrogen bonding, these vibrations also influence the shape of the IR peak. Generally, asymmetric stretching frequencies are higher than symmetric stretching frequencies. For example, primary amines exhibit two distinct IR peaks between 3300–3500 cm−1 corresponding to the symmetric and asymmetric N-H stretching, while secondary amines exhibit a single...
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Photochemical Oxidative Growth of Iridium Oxide Nanoparticles on CdSe@CdS Nanorods
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Water activation and splitting by single anionic iridium atoms.

Zhaoguo Zhu1, Gaoxiang Liu1, Sandra M Ciborowski1

  • 1Department of Chemistry, Johns Hopkins University, 3400 N Charles St., Baltimore, Maryland 21218, USA.

The Journal of Chemical Physics
|December 22, 2022
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Single anionic iridium (Ir-) efficiently activates and splits water (H2O), forming new complexes and molecular anions. This groundbreaking research reveals the first instance of water splitting by a solitary Ir- anion.

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Area of Science:

  • Inorganic Chemistry
  • Physical Chemistry
  • Surface Science

Background:

  • Water splitting is crucial for clean energy production.
  • Understanding metal-ligand interactions is key to catalysis.
  • Anionic metal complexes offer unique reactivity.

Purpose of the Study:

  • To investigate the reaction mechanism of anionic iridium with water.
  • To identify the products and intermediates of this reaction.
  • To demonstrate water activation and splitting by a single anionic iridium.

Main Methods:

  • Mass spectrometry to analyze anionic products.
  • Anion photoelectron spectroscopy to characterize complexes.
  • Computational chemistry to calculate reaction pathways and energies.

Main Results:

  • Efficient generation of [Ir(H2O)]- and IrO-.
  • Identification of three isomers of [Ir(H2O)]-: Ir-(H2O), [H-Ir-OH]-, and [H2-Ir-O]-.
  • Confirmation of an exothermic reaction pathway with singlet-triplet intersystem crossing.

Conclusions:

  • Anionic iridium is capable of activating and splitting water.
  • The reaction proceeds through distinct intermediates involving O-H bond cleavage.
  • This study opens new avenues for catalytic water splitting using anionic species.