Multimetallic complexes and functionalized nanoparticles based on unsymmetrical dithiocarbamate ligands with allyl...

Area of Science:

• Coordination Chemistry
• Organometallic Chemistry
• Materials Science

Background:

• Dithiocarbamate ligands offer versatile coordination modes and tunable electronic properties.
• Unsymmetrical dithiocarbamates with pendant functionalities are valuable building blocks for complex molecular architectures.
• Exploration of their reactivity with various transition metals is crucial for developing new functional materials.

Purpose of the Study:

• To synthesize and characterize new unsymmetrical dithiocarbamate ligands and their metal complexes.
• To investigate the reactivity of the pendant allyl and propargyl groups within these complexes.
• To explore the potential of these ligands in forming novel multinuclear complexes and nanomaterials.

Main Methods:

• Synthesis of unsymmetrical dithiocarbamate ligands (KS2CN(CH2CH═CH2)Me and KS2CN(CH2C≡CH)Me) via reaction of amines with KOH and carbon disulfide.
• Formation of homoleptic and monodithiocarbamate metal complexes with various transition metals (Ni, Pd, Pt, Ru, Au).
• Characterization of complexes using spectroscopic methods and structural studies (X-ray crystallography).
• Investigation of ligand functional group transformations (hydrogenation, cyclization) and reactivity with other metal complexes and reagents (e.g., benzylazide).

Main Results:

• Successful synthesis of novel unsymmetrical dithiocarbamate ligands and a range of their metal complexes across different transition metal groups.
• Demonstration of functional group interconversion between allyl and propargyl moieties within nickel complexes via hydrogenation.
• Observation of an atom-efficient cyclization of propargyl-dithiocarbamate ligand to form thiazolidine-2-thione derivatives.
• Formation of a trimetallic complex and a triazole-containing complex, showcasing the utility of pendant functionalities.
• Preparation of gold nanoparticles (Au@S2CN(CH2C≡CH)Me) using the propargyl dithiocarbamate ligand.

Conclusions:

• The synthesized unsymmetrical dithiocarbamates are versatile ligands for coordination chemistry.
• The pendant functionalities on the dithiocarbamate ligands enable diverse chemical transformations and the construction of complex architectures.
• These findings open avenues for designing novel organometallic compounds, multinuclear complexes, and nanomaterials with tailored properties.