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

Nucleophiles02:30

Nucleophiles

13.5K
The word “nucleophile” has a Greek root and translates to nucleus-loving. Nucleophiles are either negatively charged or neutral species with a pair of electrons in a high-energy occupied molecular orbital (HOMO). As these species tend to donate electron pairs, nucleophiles are considered Lewis bases as well. Negatively charged species, like OH−, Cl−, or HS−, with one or several pairs of electrons, are typically nucleophiles. Similarly, neutral species such as...
13.5K
Basicity of Aromatic Amines01:18

Basicity of Aromatic Amines

7.2K
The basicity of aromatic amines is much weaker than that of aliphatic amines due to the involvement of the lone pair of electrons over the N atom in resonance with the aryl rings. Generally, the electron-donating ability of any substituents on the aryl ring of aromatic amines increases the basicity of the amine by increasing electron density, and hence the availability of lone pair on the nitrogen. On the other hand, electron-withdrawing functional groups on the aryl ring of amines decrease the...
7.2K
Electrophiles02:28

Electrophiles

10.7K
This lesson explains the definition, classification, and characteristic features of an electrophile that are key features of nucleophilic substitution reactions. An analysis of their charge and orbital picture helps understand their reactivity for seeking electrons. Electrophiles can be classified into positive and neutral species. Other classes include free radicals and polar functional groups.
While a positive electrophile, like a proton, reacts due to its vacant, low-energy 1s orbital, the...
10.7K
Reactivity of Enolate Ions01:23

Reactivity of Enolate Ions

2.5K
Enolate ions are formed by the acid–base reaction of a carbonyl compound with a base. This leads to deprotonation of the α hydrogen atom, leading to a resonance-stabilized enolate ion where one of the contributing structures is an oxyanion, which imparts additional stability. Therefore, the proton on the α carbon is more acidic in nature than that of other sp3-hybridized C–H bonds but less acidic than those in O–H bonds where the negative charge in the conjugate...
2.5K
Basicity of Aliphatic Amines01:21

Basicity of Aliphatic Amines

5.9K
Amines can behave as Brønsted–Lowry bases by accepting a proton from the acid to form corresponding conjugate acids. Due to a lone pair of nonbonding electrons, aliphatic amines can also act as Lewis bases by forming a covalent bond with an electrophile.
To measure the basicity of amines, two conventions are generally used. The first defines Kb as the basicity constant for the deprotonation reaction of water by the amine, as presented in Figure 1. Conventionally, lower Kb indicates...
5.9K
Basicity of Heterocyclic Aromatic Amines01:25

Basicity of Heterocyclic Aromatic Amines

6.1K
Heterocyclic amines, where the N atom is a part of an alicyclic system, are similar in basicity to alkylamines. Interestingly, the heterocyclic amine having a nitrogen atom as part of an aromatic ring has much less basicity than its corresponding alicyclic counterpart. For this reason, as presented in Figure 1, piperidine (pKb = 2.8) is significantly more basic than pyridine (pKb = 8.8).
6.1K

You might also read

Related Articles

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

Sort by
Same author

Formation of Unusual Deprotomers of Citric Acid and Sodium Citrate Aggregates: A Photoelectron Spectroscopy and Computational Study.

The journal of physical chemistry letters·2026
Same author

Unwrapping the Dodecaborane Core: Structure, Electronic Properties, and Chemical Reactivity Across the Complete [B<sub>12</sub>I<sub><i>n</i></sub>]<sup>-</sup> Series (<i>n</i> = 11-1).

Journal of the American Chemical Society·2026
Same author

Electronic Structures and Stabilities of Trimethylsilyl-Masked Pnictogen and Chalcogen Complex Anions and Comparisons to Their Hydrides: A Combined Photoelectron Spectroscopy and Computational Study.

Inorganic chemistry·2026
Same author

Photoelectron spectroscopy and structural characterization of [EDTA · M(II)]2- · nH2O (M = Ni, Cu, Zn; n = 0-2) complexes.

The Journal of chemical physics·2026
Same author

An electrostatically enhanced bifunctional enantioselective thiourea catalyst.

Organic & biomolecular chemistry·2026
Same author

Ultrafast Electron-Dipole Interactions in TeO<sup>-</sup> Photodetachment.

The journal of physical chemistry letters·2025

Related Experiment Video

Updated: Jul 13, 2025

Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F&#8722;
06:53

Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F−

Published on: July 27, 2018

8.7K

Anion-Activated Bases and Nucleophiles Characterized by Photoelectron Spectroscopy.

Stephen H Dempsey1, Wenjin Cao2, Xue-Bin Wang2

  • 1Department of Chemistry, University of Minnesota 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.

The Journal of Physical Chemistry. A
|October 16, 2023
PubMed
Summary

New pyridine derivatives were studied using photoelectron spectroscopy and computational methods. Their electronic properties correlate with SN2 reactivity, offering a new measure of nucleophilicity for these charge-activated reagents.

More Related Videos

An Experimental Protocol for Femtosecond NIR/UV - XUV Pump-Probe Experiments with Free-Electron Lasers
09:49

An Experimental Protocol for Femtosecond NIR/UV - XUV Pump-Probe Experiments with Free-Electron Lasers

Published on: October 23, 2018

16.1K
Molecular Beam Mass Spectrometry With Tunable Vacuum Ultraviolet VUV Synchrotron Radiation
09:53

Molecular Beam Mass Spectrometry With Tunable Vacuum Ultraviolet VUV Synchrotron Radiation

Published on: October 30, 2012

13.0K

Related Experiment Videos

Last Updated: Jul 13, 2025

Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F&#8722;
06:53

Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F−

Published on: July 27, 2018

8.7K
An Experimental Protocol for Femtosecond NIR/UV - XUV Pump-Probe Experiments with Free-Electron Lasers
09:49

An Experimental Protocol for Femtosecond NIR/UV - XUV Pump-Probe Experiments with Free-Electron Lasers

Published on: October 23, 2018

16.1K
Molecular Beam Mass Spectrometry With Tunable Vacuum Ultraviolet VUV Synchrotron Radiation
09:53

Molecular Beam Mass Spectrometry With Tunable Vacuum Ultraviolet VUV Synchrotron Radiation

Published on: October 30, 2012

13.0K

Area of Science:

  • Physical Chemistry
  • Computational Chemistry
  • Organic Chemistry

Background:

  • Pyridine derivatives are versatile chemical building blocks.
  • Charge-activated anions offer unique reactivity profiles.
  • Understanding nucleophilicity is crucial for predicting reaction outcomes.

Purpose of the Study:

  • To synthesize and characterize novel pyridine derivatives with anionic substituents.
  • To investigate the electronic properties and nucleophilicity of these new reagents.
  • To establish a correlation between measured electronic properties and reactivity.

Main Methods:

  • Negative ion photoelectron spectroscopy at 20 K.
  • Ab initio coupled cluster [CCSD(T)] calculations.
  • M06-2X density functional theory (DFT) computations.

Main Results:

  • Synthesis and characterization of six basic and nucleophilic pyridine derivatives (3- and 4-PyrBX3-).
  • Measured vertical detachment energies (VDEs) range from 4.50-5.85 eV.
  • VDEs accurately predicted by CCSD(T) and M06-2X/aug-cc-pVTZ methods.
  • A surprising correlation was observed between VDEs and SN2 reactivity with 1-iodooctane.

Conclusions:

  • The study introduces a new class of charge-activated pyridine-based reagents.
  • Photoelectron spectroscopy provides an experimental measure of nucleophilicity for these anions.
  • The findings link electronic structure to chemical reactivity, aiding reagent design.