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Related Concept Videos

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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[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement01:21

[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement

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The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
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Structural Isomerism02:34

Structural Isomerism

22.4K
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
22.4K
Aryldiazonium Salts to Azo Dyes: Diazo Coupling01:11

Aryldiazonium Salts to Azo Dyes: Diazo Coupling

4.1K
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 para...
4.1K
Aldehydes and Ketones with HCN: Cyanohydrin Formation Overview01:32

Aldehydes and Ketones with HCN: Cyanohydrin Formation Overview

4.3K
Cyanohydrins are compounds that contain –CN and –OH groups on the same carbon atom. They are formed by the nucleophilic addition of the cyanide ions to the carbonyl group. Cyanide ions are highly basic and nucleophilic and can be generated from HCN under aqueous conditions. However, since HCN is a weak acid, the number of cyanide ions generated is very small. Hence, a small amount of base or KCN/NaCN is added to HCN to increase the concentration of the cyanide ions in the reaction...
4.3K
Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism01:10

Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism

4.8K
Cyanohydrins are formed when cyanide nucleophiles and carbonyl compounds like aldehydes and ketones react. A strong base, the cyanide ion, catalyzes cyanohydrin formation. The ions are generated from HCN under aqueous conditions. Once the cyanide ions are generated, the first step involves the nucleophilic attack of the cyanide ions on the electrophilic carbonyl carbon. This attack shifts the π electrons from the C=O to the oxygen atom forming the alkoxide ion intermediate. The alkoxide anion...
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Related Experiment Video

Updated: Apr 3, 2026

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

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Hydrazine-mediated strongly coupled Re(CO)3 dimers.

A Hasheminasab1, H M Rhoda, L A Crandall

  • 1Department of Chemistry, University of Akron, OH 44325-3601, USA. ziegler@uakron.edu.

Dalton Transactions (Cambridge, England : 2003)
|September 17, 2015
PubMed
Summary

Two rhenium (Re) dimers linked by a Schiff base ligand show strong electronic coupling. This coupling, confirmed by electrochemistry and computational methods, originates from the ligand, not the metal centers.

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Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions
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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
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Area of Science:

  • Inorganic Chemistry
  • Electrochemistry
  • Computational Chemistry

Background:

  • Dimeric metal complexes can display coupling interactions mediated by bridging ligands.
  • Schiff base ligands are versatile in coordinating metal ions and influencing their electronic properties.

Purpose of the Study:

  • To synthesize and characterize two rhenium(III) carbonyl dimers bridged by a bis(pyridine-2-carbaldehyde imine) hydrazine ligand.
  • To investigate the electronic coupling and redox behavior of these dimeric complexes.
  • To elucidate the electronic structure and the origin of the observed coupling using computational methods.

Main Methods:

  • Synthesis of rhenium(III) carbonyl dimers.
  • Cyclic voltammetry to study redox properties and electronic coupling.
  • Spectroelectrochemistry to detect mixed-valence states and inter-valence charge-transfer (IVCT) bands.
  • Density Functional Theory (DFT) and Time-Dependent DFT (TDDFT) for electronic structure calculations.

Main Results:

  • Successful synthesis of two Re(CO)3 dimers linked by a bis(pyca) hydrazine Schiff base ligand.
  • Observation of strong electronic coupling across the dimer, evidenced by large separation in reduction potentials (∼480 mV) and high comproportionation constants (∼1.5 × 10^8).
  • Spectroelectrochemistry confirmed a mixed-valence state upon reduction, with a distinct IVCT band.
  • DFT calculations revealed that reduction occurs at the diimine units, indicating ligand-based electronic coupling.

Conclusions:

  • The bis(pyca) hydrazine Schiff base ligand effectively mediates strong electronic coupling between the two rhenium centers in the dimeric complexes.
  • The observed coupling is primarily a ligand-based phenomenon, influencing the electronic communication between the metal centers.
  • The study provides insights into the design of multinuclear complexes with tunable electronic properties through ligand choice.