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Nitrous acid, a weak acid, is prepared in situ via the reaction of sodium nitrite with a strong acid under cold conditions. This nitrous acid prepared in situ reacts with primary arylamines to form arenediazonium salts. Such reactions are known as diazotization reactions. As shown in Figure 1, the formation of arenediazonium salts begins with the decomposition of nitrous acid in an acidic solution to give nitrosonium ions.
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Pd8(PDip)6: Cubic, Unsaturated, Zerovalent.

Kevin Breitwieser1, Matteo Bevilacqua1,2, Sneha Mullassery1

  • 1Coordination Chemistry Saarland University, Campus C4.1, D-66123, Saarbrücken, Germany.

Advanced Science (Weinheim, Baden-Wurttemberg, Germany)
|April 18, 2024
PubMed
Summary
This summary is machine-generated.

Researchers synthesized a novel palladium nanocluster, Pd8(PDip)6, using triphosphirane. This air-stable cluster exhibits unique electronic properties and can rearrange upon binding molecules, showing potential for advanced materials.

Keywords:
atomically preciseclustercubephosphinideneunsaturation

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Area of Science:

  • Nanomaterials Science
  • Supramolecular Chemistry
  • Organometallic Chemistry

Background:

  • Atomically precise nanoclusters are key building blocks for advanced materials.
  • Palladium nanoclusters offer potential in optoelectronics and magnetism.
  • Developing stable and manipulable nanoclusters is crucial for their application.

Purpose of the Study:

  • To synthesize and characterize a novel palladium nanocluster.
  • To investigate the electronic structure and reactivity of the nanocluster.
  • To explore the potential of the nanocluster in supramolecular assembly.

Main Methods:

  • Synthesis of Pd8(PDip)6 from palladium(0) precursors and triphosphirane.
  • Characterization using mass spectrometry, NMR, IR, UV-vis, XP spectroscopies, and sc-XRD.
  • Cyclovoltammetry and quantum chemical calculations to study electronic properties.
  • Trapping experiments to elucidate cluster growth and rearrangement mechanisms.

Main Results:

  • A stable, strongly colored, coordinatively unsaturated 104-electron Pd(0) cluster with a cubic Pd8-core and µ4-capping phosphinidene ligands was synthesized.
  • Electronic structure analysis revealed 5s/4d orbital mixing and Pd-P covalency.
  • Cluster growth occurs via insertion of Pd(0) into the triphosphirane.
  • The nanocluster senses ethylene and binds isocyanides, inducing rearrangement to a tetrahedral structure with a reduced energy gap.

Conclusions:

  • Facile synthesis of a novel, air-stable palladium nanocluster.
  • Demonstrated manipulation and non-destructive rearrangement of the nanocluster.
  • Highlights the potential of Pd8(PDip)6 for supramolecular assembly and functional materials.