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Stereoisomerism

Stereoisomerism

Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...

Thermal Electrocyclic Reactions: Stereochemistry

Thermal Electrocyclic Reactions: Stereochemistry

The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.

Lattice Energies of Ionic Crystals

Lattice Energies of Ionic Crystals

Lattice energy represents the energy released when gaseous cations and anions combine to form an ionic solid, reflecting the strength of electrostatic interactions within the crystal. This process is fundamentally governed by Coulombic attraction between oppositely charged ions, where the potential energy varies inversely with the interionic distance and directly with the product of ionic charges. As ions approach one another, the electrostatic energy becomes increasingly negative, indicating a...

Molecular Orbital Theory II

Molecular Orbital Theory II

Molecular Orbital Energy Diagrams

Stereoisomerism of Cyclic Compounds

Stereoisomerism of Cyclic Compounds

In this lesson, we delve into the role of ring conformation and its stability, which determines the spatial arrangement and, consequently, the molecular symmetry and stereoisomerism of cyclic compounds. 1,2-Dimethylcyclohexane is used as a case study to evaluate the possible number of stereoisomers. Here, given the multiple (n = 2) chiral centers, there are 2n = 4 possible configurations that lack a plane of symmetry, as the ring skeleton exists in a non-planar chair conformation. In addition,...

Crystal Field Theory - Octahedral Complexes

Crystal Field Theory - Octahedral Complexes

Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...

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Related Experiment Video

Updated: May 15, 2026

Coulomb Explosion Imaging as a Tool to Distinguish Between Stereoisomers

Coulomb Explosion Imaging as a Tool to Distinguish Between Stereoisomers

Published on: August 18, 2017

Isomerization energy decomposition analysis for highly ionic systems: case study of starlike E5Li7(+) clusters.

Maryel Contreras¹, Edison Osorio, Franklin Ferraro

¹Departamento de Química, Universidad de Guanajuato, Noria Alta s/n 36050 Guanajuato, Mexico.

Chemistry (Weinheim an Der Bergstrasse, Germany)

|January 8, 2013

Summary

Researchers studied stable forms of E(5)Li(7)(+) clusters (E = Ge, Sn, Pb) using a stochastic search. Germanium clusters preferred a starlike structure, while tin and lead clusters adopted different configurations.

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Last Updated: May 15, 2026

Coulomb Explosion Imaging as a Tool to Distinguish Between Stereoisomers

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Published on: August 18, 2017

Spatial Separation of Molecular Conformers and Clusters

Spatial Separation of Molecular Conformers and Clusters

Published on: January 9, 2014

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

Published on: April 8, 2020

Area of Science:

Computational chemistry
Cluster science
Materials science

Background:

Investigating the structures of small metal clusters is crucial for understanding their chemical properties.
The behavior of heavy elements like tin and lead in clusters often deviates from lighter analogues.
Previous studies on C(5)Li(7)(+) and Si(5)Li(7)(+) provided a basis for comparison.

Purpose of the Study:

To determine the most stable structural isomers of E(5)Li(7)(+) clusters where E represents Germanium (Ge), Tin (Sn), and Lead (Pb).
To elucidate the factors governing the structural preferences of these heavy element lithium clusters.
To introduce and apply a novel energy decomposition analysis method for isomerizations.

Main Methods:

Utilizing a stochastic search of potential-energy surfaces via the gradient embedded genetic algorithm (GEGA).
Employing isomerization energy decomposition analysis (IEDA) to analyze energetic differences between isomers.
Comparing the structural outcomes for Ge, Sn, and Pb within the E(5)Li(7)(+) framework.

Main Results:

The Ge(5)Li(7)(+) cluster favors a distorted starlike structure, similar to lighter clusters.
Sn(5)Li(7)(+) and Pb(5)Li(7)(+) exhibit significantly different preferred structures compared to Ge(5)Li(7)(+).
Lowest-energy structures for Sn and Pb involve out-of-plane migration of the E atom and Li atom rearrangement.

Conclusions:

Structural preferences in E(5)Li(7)(+) clusters are element-dependent, with heavier elements showing distinct behavior.
The proposed IEDA method effectively extracts energetic insights from isomerizations in highly charged fragments.
Computational modeling and advanced analysis are key to understanding complex cluster structures and their stability.