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Related Concept Videos

Thermal Sigmatropic Reactions: Overview01:16

Thermal Sigmatropic Reactions: Overview

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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...
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The axial and equatorial protons in cyclohexane can be distinguished by performing a variable-temperature NMR experiment. In this process, except for one proton, the remaining eleven protons are replaced by deuterium. The deuterium substitution avoids the possible peak splitting caused by the spin-spin coupling between the adjacent protons. The remaining proton flips between the axial and equatorial positions.
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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
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Intermolecular forces are attractive forces that exist between molecules. They dictate several bulk properties, such as melting points, boiling points, and solubilities (miscibilities) of substances. Molar mass, molecular shape, and polarity affect the strength of different intermolecular forces, which influence the magnitude of physical properties across a family of molecules.
Temporary attractive forces like dispersion are present in all molecules, whether they are polar or nonpolar. They...
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Aromatic Hydrocarbon Cations: Structural Overview01:18

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Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
Removing one hydrogen from the intervening CH2 group...
2.9K
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Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
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Thermal Polymorphism in CsCB11H12.

Radovan Černý1, Matteo Brighi1, Hui Wu2

  • 1Laboratory of Crystallography, Department of Quantum Matter Physics, University of Geneva, Quai Ernest-Ansermet 24, CH-1211 Geneva, Switzerland.

Molecules (Basel, Switzerland)
|March 11, 2023
PubMed
Summary
This summary is machine-generated.

Cesium CB11H12 exhibits complex thermal polymorphism with multiple phases. Its anion undergoes isotropic rotational diffusion, similar to lighter alkali-metal salts, indicating potential for superionic conductivity.

Keywords:
anion dynamicscrystal structuremonocarba-hydridoboratepolymorphism

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Area of Science:

  • Solid-state chemistry
  • Materials science
  • Crystallography

Background:

  • Alkali-metal salts of the icosohedral monocarba-hydridoborate anion (CB11H12-) show thermal polymorphism and superionic conductivity.
  • Previous studies focused on LiCB11H12 and NaCB11H12, with less attention on heavier analogues like CsCB11H12.
  • Understanding structural arrangements across the alkali-metal series is crucial for comparative analysis.

Purpose of the Study:

  • To investigate the thermal polymorphism of cesium CB11H12 (CsCB11H12).
  • To characterize the structural behavior and dynamical properties of CsCB11H12 across a temperature range.
  • To compare the properties of CsCB11H12 with lighter alkali-metal CB11H12- salts.

Main Methods:

  • X-ray powder diffraction
  • Differential scanning calorimetry
  • Raman, infrared, and neutron spectroscopies
  • Ab initio calculations
  • Quasielastic neutron scattering

Main Results:

  • Anhydrous CsCB11H12 displays unexpected temperature-dependent structural behavior, suggesting the presence of multiple polymorphs.
  • Two main polymorph scenarios were proposed: one involving ordered R3 transforming to R3c and then disordered I43d, and another with a disordered Fm3 phase appearing from I43d.
  • Quasielastic neutron scattering revealed isotropic rotational diffusion of CB11H12- anions in the disordered phase at 560 K, with a jump correlation frequency comparable to lighter analogues.

Conclusions:

  • CsCB11H12 exhibits complex thermal polymorphism with multiple phases and transitions.
  • The observed anion dynamics in CsCB11H12 are consistent with those in superionic lighter alkali-metal analogues.
  • This study provides fundamental insights into the structural and dynamical properties across the alkali-metal CB11H12- series.