Jove
Visualize
Contact Us
JoVE
x logofacebook logolinkedin logoyoutube logo
ABOUT JoVE
OverviewLeadershipBlogJoVE Help Center
AUTHORS
Publishing ProcessEditorial BoardScope & PoliciesPeer ReviewFAQSubmit
LIBRARIANS
TestimonialsSubscriptionsAccessResourcesLibrary Advisory BoardFAQ
RESEARCH
JoVE JournalMethods CollectionsJoVE Encyclopedia of ExperimentsArchive
EDUCATION
JoVE CoreJoVE BusinessJoVE Science EducationJoVE Lab ManualFaculty Resource CenterFaculty Site
Terms & Conditions of Use
Privacy Policy
Policies

Related Concept Videos

[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement01:21

[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement

2.7K
The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
2.7K
Photochemical Electrocyclic Reactions: Stereochemistry01:26

Photochemical Electrocyclic Reactions: Stereochemistry

1.8K
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
1.8K
Thermal Sigmatropic Reactions: Overview01:16

Thermal Sigmatropic Reactions: Overview

2.1K
Sigmatropic rearrangements are a class of pericyclic reactions in which a σ bond migrates from one part of a π system to another. These are intramolecular rearrangements where the total number of σ and π bonds remain unchanged.
Sigmatropic shifts are classified based on an order term [i, j ], where i and j indicate the number of atoms across which each end of the σ bond migrates. Below are examples of a [3,3] sigmatropic shift in...
2.1K
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH301:11

ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3

6.0K
All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...
6.0K
Thermal and Photochemical Electrocyclic Reactions: Overview01:26

Thermal and Photochemical Electrocyclic Reactions: Overview

2.3K
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
2.3K
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions01:20

Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions

1.9K
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...
1.9K

You might also read

Related Articles

Articles linked to this work by shared authors, journal, and citation graph.

Sort by
Same author

Unveiling Excited-State Dynamics of Nitrobenzene through Time-Resolved X-ray Absorption Spectroscopy.

The journal of physical chemistry letters·2026
Same author

Electrochemical Strain-Release Difunctionalization of Azabicyclo-[1.1.0]butanes with Nitroarenes.

Journal of the American Chemical Society·2026
Same author

Structural basis of FatB-mediated iron uptake via tyrosine/histidine direct coordination accompanying long-distance domain reorganization.

Nature communications·2026
Same author

Transition-Metal Hydride Catalysis Meets Nitrenoid Transfer: Design Principles for Precision C-N Bond Formation.

Accounts of chemical research·2026
Same author

Rapid and Stereoselective Ring-Opening Polymerization of rac-Lactide Enabled by a Chiral Cyclopropenimine-Thiourea Catalyst.

Angewandte Chemie (International ed. in English)·2026
Same author

Solvent-accelerated photoreduction of Hg(II) dihalides: uncovering solvent-governed and light-triggered mercury chemistry.

Physical chemistry chemical physics : PCCP·2026

Related Experiment Video

Updated: Jun 24, 2025

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization
12:19

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization

Published on: November 29, 2018

8.5K

Photoinduced Group Transposition via Iridium-Nitrenoid Leading to Amidative Inner-Sphere Aryl Migration.

Hoimin Jung1,2, Jungkweon Choi3,2, Daniel Kim1,2

  • 1Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon, 34141, Republic of Korea.

Angewandte Chemie (International Ed. in English)
|June 13, 2024
PubMed
Summary

This study reveals how organometallic photoprecursors generate metal-nitrenoids upon light activation. This process enables a novel amidative group transposition via inner-sphere aryl migration.

Keywords:
IridiumNitrenoidsOrganometallicsPhotochemistryReaction mechanisms

More Related Videos

Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene
09:45

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

Published on: March 20, 2017

10.4K
[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
09:12

[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

Published on: May 21, 2019

9.2K

Related Experiment Videos

Last Updated: Jun 24, 2025

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization
12:19

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization

Published on: November 29, 2018

8.5K
Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene
09:45

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

Published on: March 20, 2017

10.4K
[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
09:12

[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

Published on: May 21, 2019

9.2K

Area of Science:

  • Organometallic Chemistry
  • Photochemistry
  • Reaction Mechanisms

Background:

  • Photochemical generation of reactive intermediates is crucial for synthetic transformations.
  • Understanding metal-nitrenoid reactivity is key to developing new catalytic cycles.
  • Inner-sphere ligand migration offers unique pathways for functional group transfer.

Purpose of the Study:

  • To investigate the fundamental mechanism of photochemical metal-nitrenoid generation.
  • To explore the inner-sphere transposition reactivity of organometallic photoprecursors.
  • To elucidate the role of metal-to-ligand charge transfer in ligand activation and migration.

Main Methods:

  • Synthesis and characterization of Cp*Ir(hydroxamate)(Ar) complexes.
  • Photo-initiation studies combined with femtosecond transient absorption spectroscopy.
  • Density functional theory (DFT) calculations to model reaction pathways.

Main Results:

  • Photo-initiated ligand activation of Cp*Ir(hydroxamate)(Ar) complexes.
  • Demonstration of metal-to-ligand charge transfer facilitating σ(N-O) bond cleavage.
  • Observation of Ir-acylnitrenoid generation and subsequent inner-sphere σ(Ir-aryl) migration.

Conclusions:

  • A novel photochemical pathway for generating metal-nitrenoids has been established.
  • The study reveals a unique amidative group transposition driven by inner-sphere aryl migration.
  • Mechanistic insights were gained into photo-initiated ligand activation and reactivity.