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Characterizing Lewis Pairs Using Titration Coupled with In Situ Infrared Spectroscopy
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Lewis Base Supported Terminal Thorium Imido Metallocene [η5-1,3-(Me3C)2C5H3]2Th(═Ndipp)(dmap): Its Synthesis,

Dongwei Wang1, Yi Heng1, Guohua Hou1

  • 1Department of Chemistry, Beijing Normal University, Beijing 100875, China.

Inorganic Chemistry
|March 20, 2025
PubMed
Summary
This summary is machine-generated.

Thorium imido metallocene, (Cp2)2Th(═Ndipp)(dmap), was synthesized and found to be a versatile synthon. It activates various unsaturated substrates and undergoes deprotonation reactions, showcasing tunable reactivity.

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Area of Science:

  • Organometallic Chemistry
  • Thorium Chemistry
  • Ligand Design

Background:

  • Thorium metallocenes are important in organometallic chemistry.
  • The synthesis and reactivity of thorium imido complexes are less explored.
  • Understanding ligand effects is crucial for controlling reactivity.

Purpose of the Study:

  • To synthesize a Lewis base-supported terminal thorium imido metallocene.
  • To investigate the reactivity of the synthesized thorium imido complex as a synthon.
  • To explore the influence of ligand substituents on reactivity.

Main Methods:

  • Synthesis of thorium imido metallocene via addition of dippNH2 to thorium dimethyl metallocene.
  • Reactions of the thorium imido complex with various unsaturated substrates (alkynes, ketones, CS2, etc.).
  • Deprotonation reactions with different organic molecules (thiazole, nitriles, etc.).
  • Formation of heterobimetallic complexes.
  • Analysis of substituent effects on cyclopentadienyl and imido ligands.

Main Results:

  • Successful synthesis of Lewis base-supported terminal thorium imido metallocene, (Cp2)2Th(═Ndipp)(dmap).
  • The complex acts as a synthon for the (Cp2)2Th(II) fragment.
  • Demonstrated broad reactivity including activation of diverse unsaturated compounds and deprotonation reactions.
  • Formation of various complexes: pyridyl alkenyl, oxido, sulfido, selenido, alkoxido amidate, metallacycles, bis-amido, dichloride, amido thiazolyl, bis-alkynyl, amido enolyl, bis-amidates, amido-iminato, amido pyridyl, iminato, and bis-amido complexes.
  • Cannizarro-type reaction with aldehydes and Friedel-Crafts alkylation with organic azides observed.
  • Formation of a heterobimetallic complex with CuCl.
  • Substituent effects on ligands were probed to modulate reactivity.

Conclusions:

  • The synthesized thorium imido metallocene is a versatile reagent in organothorium chemistry.
  • Its reactivity can be tuned by modifying ligand substituents.
  • This study expands the synthetic utility of thorium imido complexes.