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¹H NMR: Long-Range Coupling01:27

¹H NMR: Long-Range Coupling

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The coupling interactions of nuclei across four or more bonds are usually weak, with J values less than 1 Hz. While these are usually not observed in spectra, the presence of multiple bonds along the coupling pathway can result in observable long-range coupling.
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene...
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Two NMR-active nuclei bonded to a central atom can be involved in geminal or two-bond coupling. Geminal coupling is commonly seen between diastereotopic protons in chiral molecules and unsymmetrical alkenes, among others.
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
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Aryldiazonium Salts to Azo Dyes: Diazo Coupling01:11

Aryldiazonium Salts to Azo Dyes: Diazo Coupling

3.1K
The reaction of weakly electrophilic aryldiazonium (also called arenediazonium) salts with highly activated aromatic compounds leads to the formation of products with an —N=N— link, called an azo linkage. This reaction, presented in Figure 1, is known as diazo coupling and occurs without the loss of the nitrogen atoms of the aryldiazonium salt. Highly activated aromatic compounds such as phenols or arylamines favor the diazo coupling reaction. The coupling generally occurs at the...
3.1K
Vicinal Diols via Reductive Coupling of Aldehydes or Ketones: Pinacol Coupling Overview01:27

Vicinal Diols via Reductive Coupling of Aldehydes or Ketones: Pinacol Coupling Overview

1.8K
Wilhelm Rudolph Fittig discovered the pinacol coupling reaction in 1859. It is a radical dimerization reaction and involves the reductive coupling of aldehydes or ketones in the presence of hydrocarbon solvent to yield vicinal diols.
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Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)01:22

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1.2K
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...
1.2K
Metal-Semiconductor Junctions01:24

Metal-Semiconductor Junctions

547
The contact of metal and semiconductor can lead to the formation of a junction with either Schottky or Ohmic behavior.
Schottky Barriers
Schottky barriers arise when a metal with a work function (Φm) contacts a semiconductor with a different work function (Φs). Initially, electrons transfer until the Fermi levels of the metal and semiconductor align at equilibrium. For instance, if Φm > Φs, the semiconductor Fermi level is higher than the metal's before contact. The...
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Phenylene as an efficient mediator for intermetallic electronic coupling.

Lyndsy A Miller-Clark1, Adharsh Raghavan1, Reese A Clendening1

  • 1Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA. tren@purdue.edu.

Chemical Communications (Cambridge, England)
|April 13, 2022
PubMed
Summary
This summary is machine-generated.

A new ruthenium compound bridged by 1,4-phenylene demonstrates strong electronic coupling. This coupling allows for rapid hole delocalization between metal centers, confirmed by spectroelectrochemistry and DFT analysis.

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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Supramolecular Chemistry

Background:

  • Investigating electronic communication through bridging ligands is crucial for designing advanced materials.
  • The role of phenylene bridges in mediating intermetallic electronic coupling remains an area of active research.

Purpose of the Study:

  • To synthesize and characterize a new dinuclear ruthenium compound with a 1,4-phenylene bridge.
  • To determine if the 1,4-phenylene bridge can mediate electronic coupling between the two Ru2 units.
  • To elucidate the mechanism of electronic coupling.

Main Methods:

  • Synthesis of the dinuclear ruthenium compound [(NC)Ru2(ap)4]2(μ-1,4-C6H4).
  • Spectroelectrochemistry to probe electronic delocalization on the IR time scale.
  • Density Functional Theory (DFT) analysis to understand the orbital mechanism of coupling.

Main Results:

  • Successful preparation of the target dinuclear ruthenium complex.
  • Evidence of strong electronic coupling and hole delocalization between Ru2 centers on the femtosecond timescale.
  • DFT calculations provided insights into the orbital interactions responsible for the observed coupling.

Conclusions:

  • The 1,4-phenylene bridge effectively mediates strong electronic coupling between dinuclear ruthenium centers.
  • Hole delocalization occurs rapidly, indicating efficient electronic communication.
  • The study provides a fundamental understanding of electronic coupling mechanisms in bridged metal complexes.