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Related Concept Videos

Thermal Electrocyclic Reactions: Stereochemistry01:17

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.
Valence Bond Theory02:42

Valence Bond Theory

Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
Valence Bond Theory02:45

Valence Bond Theory

Overview of Valence Bond Theory
Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)01:22

Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)

Vicinal or three-bond coupling is commonly observed between protons attached to adjacent carbons. Here, nuclear spin information is primarily transferred via electron spin interactions between adjacent C‑H bond orbitals. This generally favors the antiparallel arrangement of spins, so 3J values are usually positive.
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the involved orbitals. The...
Aromatic Hydrocarbon Cations: Structural Overview01:18

Aromatic Hydrocarbon Cations: Structural Overview

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 with both...
Photochemical Electrocyclic Reactions: Stereochemistry01:26

Photochemical Electrocyclic Reactions: Stereochemistry

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

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Related Experiment Video

Updated: Jul 3, 2026

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
10:52

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex

Published on: July 27, 2022

Ti(IV)-centered dynamic interconversion between Pd(II), Ti(IV)-containing ring and cage molecules.

Shuichi Hiraoka1, Yoko Sakata, Mitsuhiko Shionoya

  • 1Department of Chemistry, Graduate School of Science, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan. hiraoka@chem.s.u-tokyo.ac.jp

Journal of the American Chemical Society
|July 11, 2008
PubMed
Summary
This summary is machine-generated.

Researchers created novel supramolecular complexes using a pyridyl catechol ligand, titanium, and palladium. These complexes are interconvertible, showcasing dynamic Ti4+-centered coordination changes driven by component fraction and basicity.

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Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liquid
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Using Cyclic Voltammetry, UV-Vis-NIR, and EPR Spectroelectrochemistry to Analyze Organic Compounds
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Using Cyclic Voltammetry, UV-Vis-NIR, and EPR Spectroelectrochemistry to Analyze Organic Compounds
11:44

Using Cyclic Voltammetry, UV-Vis-NIR, and EPR Spectroelectrochemistry to Analyze Organic Compounds

Published on: October 18, 2018

Area of Science:

  • Coordination Chemistry
  • Supramolecular Chemistry
  • Materials Science

Background:

  • Supramolecular chemistry focuses on non-covalent interactions to build complex structures.
  • Heteronuclear complexes offer unique properties due to the presence of multiple metal centers.
  • Titanium and palladium complexes are widely studied for their catalytic and structural applications.

Purpose of the Study:

  • To construct novel heteronuclear, supramolecular ring and cage complexes.
  • To investigate the interconvertibility between different Ti4+-centered coordination structures.
  • To understand the factors influencing Ti4+-centered structural transformations.

Main Methods:

  • Synthesis of heteronuclear complexes using a pyridyl catechol ligand, TiO(acac)2, and PdCl2(CH3CN)2.
  • Spectroscopic and crystallographic analyses to characterize the complexes.
  • Investigation of reaction conditions, including component fraction and basicity, to study interconversion.

Main Results:

  • Successfully constructed heteronuclear, supramolecular ring and cage complexes.
  • Demonstrated quantitative interconversion between two distinct Ti4+-centered coordination structures: Ti(catecholato)3 and TiH(catecholato)2(acetylacetonato).
  • Identified component fraction and basicity as key factors driving the Ti4+-centered structural changes.

Conclusions:

  • The study presents novel heteronuclear supramolecular complexes with dynamic Ti4+-centered coordination.
  • The interconversion mechanism provides insights into the flexibility and responsiveness of these complexes.
  • Findings contribute to the understanding of self-assembly and structural diversity in coordination chemistry.