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Conformations of Cyclohexane02:11

Conformations of Cyclohexane

15.0K
Cyclohexane does not exist in a planar form due to the high angle and torsional strain it would experience in the planar structure. Instead, it adopts non-planar chair and boat conformations.
The chair form is the most stable and derives its name from its resemblance to the “easy chair.” In the chair conformation, two carbon atoms are arranged out-of-plane — one above and one below, minimizing the torsional strain. In the chair form, the bond angle is very close to the ideal...
15.0K
Conformations of Cycloalkanes02:29

Conformations of Cycloalkanes

13.9K
Adolf von Baeyer attempted to explain the instabilities of small and large cycloalkane rings using the concept of angle strain — the strain caused by the deviation of bond angles from the ideal 109.5° tetrahedral value for sp3  hybridized carbons. However, while cyclopropane and cyclobutane are strained, as expected from their highly compressed bond angles, cyclopentane is more strained than predicted, and cyclohexane is virtually strain-free. Hence, Baeyer’s theory that...
13.9K
Benzene to Phenol via Cumene: Hock Process01:27

Benzene to Phenol via Cumene: Hock Process

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The synthesis of phenol from benzene via cumene and cumene hydroperoxide is called the Hock process. First, a Friedel–Crafts alkylation reaction of benzene with propene gives cumene. Then cumene forms cumene hydroperoxide via a radical chain reaction. In the chain initiation step, the benzylic hydrogen is abstracted to give a benzylic radical. In the chain propagation step, the benzylic radical reacts with an oxygen diradical to form a cumene hydroperoxide radical. The cumene...
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Chair Conformation of Cyclohexane02:02

Chair Conformation of Cyclohexane

17.7K
The chair conformation is the most stable form of cyclohexane due to the absence of angle and torsional strain. The absence of angle strain is a result of cyclohexane’s bond angle being very close to the ideal tetrahedral bond angle of 109.5° in its chair conformer. Similarly, the torsional strain is also absent owing to the perfectly staggered arrangement of bonds.
The hydrogen atoms linked to carbons are arranged in two different axial and equatorial orientations to achieve this...
17.7K
Structure of Conjugated Dienes01:16

Structure of Conjugated Dienes

6.6K
Introduction
Conjugated dienes are compounds characterized by the presence of alternating double and single bonds. In a conjugated system like 1,3-butadiene, the unhybridized 2p orbital on each carbon overlaps continuously, allowing the π electrons to be delocalized across the entire molecule. In contrast, this type of overlap does not occur in cumulated and isolated dienes, such as 2,3-pentadiene and 1,4-pentadiene, respectively. Instead, the π electrons remain localized between the double...
6.6K
Bending01:10

Bending

766
Pure bending is a fundamental concept in structural mechanics, essential for understanding how materials deform under symmetrical loads without direct forces. Pure bending occurs when prismatic members, such as beams, are subjected to equal and opposite moments that induce bending. The phenomenon is crucial as it allows for predicting stress distributions without the influence of axial or shear forces.
In pure bending, the bending stress in a beam is calculated based on the bending moment and...
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Updated: Dec 30, 2025

Preparation of a Corannulene-functionalized Hexahelicene by CopperI-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units
09:35

Preparation of a Corannulene-functionalized Hexahelicene by CopperI-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units

Published on: September 18, 2016

12.0K

How to Bend a Cumulene.

José Enrique Barquera-Lozada1

  • 1Instituto de Química, Universidad Nacional Autónoma de México, Circuito exterior, Ciudad Universitaria Coyoacán, México, D.F., 04510, Mexico.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|January 26, 2020
PubMed
Summary

N-heterocyclic carbene terminal groups can significantly bend linear [4]cumulenes, creating a stable, delocalized structure. These bent cumulenes are substantially more stable than their linear counterparts.

Keywords:
carbenescarboncumulenesdensity functional calculationsnitrogen heterocycles

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

  • Organic Chemistry
  • Computational Chemistry

Background:

  • Allenes and [n]cumulenes are linear carbon chains.
  • Terminal groups with carbene nature can induce bending in these structures.
  • N-heterocyclic carbenes (NHCs) and cyclic (alkyl)(amino) carbenes (CAACs) are known for their unique electronic properties.

Purpose of the Study:

  • To analyze how NHC and CAAC terminal groups influence the linearity of [n]cumulenes.
  • To investigate the structural and stability properties of carbene-modified cumulenes.
  • To explore the potential for synthesizing novel, bent cumulene structures.

Main Methods:

  • Density Functional Theory (DFT) calculations were employed.
  • Analysis of electronic structure and molecular geometry.
  • Comparison of stability between different [n]cumulene systems.

Main Results:

  • NHC terminal groups induce significant bending in [4]cumulenes, forming a highly non-linear structure.
  • The bent NHC [4]cumulene exhibits delocalized π electrons and enhanced stability.
  • NHC [2n]cumulenes are predicted to be over 25 kcal/mol more stable than [2n-1]cumulenes.
  • Bent [4]cumulenes are more stable than previously elusive [3]cumulenes.

Conclusions:

  • NHC and CAAC terminal groups can dramatically alter the geometry of [n]cumulenes, favoring bent structures.
  • The electronic properties of NHCs lead to exceptionally stable, bent [4]cumulenes.
  • These findings open avenues for the synthesis of novel, stable cumulene derivatives.