Terbium and Vanadium Metal Nanoparticles Reactive Starting Materials for Liquid-Phase Syntheses.

Area of Science:

• Inorganic Chemistry
• Materials Science
• Nanotechnology

Background:

• Lanthanide and early transition metals exhibit limited reactivity due to surface area, solubility, and passivation issues.
• Small-sized metal nanoparticles offer enhanced reactivity, enabling reactions in the liquid phase near room temperature.

Purpose of the Study:

• To synthesize and characterize highly reactive terbium (Tb) and vanadium (V) metal nanoparticles.
• To explore the reactivity of these nanoparticles in liquid-phase reactions with cyclopentadienyl and carbonyl precursors.
• To obtain novel compounds featuring metal-metal bonding and low-valent metal centers.

Main Methods:

• Synthesis of Tb and V nanoparticles via reduction of TbCl3 and VCl3 precursors in THF.
• Liquid-phase reactions of Tb(0)/V(0) nanoparticles with [Cp2MCl2] and [M(CO)6] (M = Mo, W) in various solvents.
• Extensive characterization using Transmission Electron Microscopy (TEM), X-ray Diffraction (XRD), Fourier-Transform Infrared Spectroscopy (FT-IR), Density Functional Theory (DFT), Mass Spectrometry (MS), and Electron Spin Resonance (ESR).

Main Results:

• Successful preparation of Tb (2.8 nm) and V (1.2 nm) metal nanoparticles with distinct reactivities.
• Formation of novel compounds including [BMIm][Cp2Mo(GaCl3)2], [BMIm][Cp2W(GaCl3)2], [Cp2Mo{GaCl2(THF)}2], [BMIm][Cp2MoGa2Cl5], [VO(H2Cyclal)Mo(CO)4], and [VO(H2Cyclal)W(CO)4].
• These compounds exhibit metal-metal bonding (Mo-Ga, W-Ga) and/or low-valent metal states (Mo(0/I), W(0/I), Ga(III)).

Conclusions:

• Tb(0)/V(0) nanoparticles provide a powerful platform for accessing unique chemical reactivity distinct from their bulk counterparts.
• This novel redox approach facilitates the synthesis of metal-metal bonded compounds and low-valent metal complexes.
• The findings open new avenues for designing and synthesizing advanced inorganic materials with tailored electronic and bonding properties.