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

Lanthanide metals and early transition metals - although in principle highly reactive - only show a limited reactivity due to small surface, low solubility, and/or passivation. To this regard, small-sized metal nanoparticles can give the opportunity for reactions near room temperature in the liquid phase. With terbium-metal nanoparticles (2.8 ± 0.4 nm) and vanadium-metal nanoparticles (1.2±0.2 nm), representative lanthanide and early-transition metals are presented with different reactivity. Both are prepared by reduction of simple precursors (TbCl₃, VCl₃) in THF. The Tb(0)/V(0) nanoparticles are highly reactive and used as starting materials in the liquid phase (THF, toluene, n-dodecane, ionic liquid) to perform reactions with cyclopentadienyl precursors [Cp₂MCl₂] and carbonyl precursors [M(CO)₆] (M = Mo, W). As a result, the novel compounds [BMIm][Cp₂Mo(GaCl₃)₂] 1), [BMIm][Cp₂W(GaCl₃)₂] 2), [Cp₂Mo{GaCl₂(THF)}₂] 3), [BMIm][Cp₂MoGa₂Cl₅] 4), [VO(H₂Cyclal)Mo(CO)₄] 5) and [VO(H₂Cyclal)W(CO)₄] 6) are obtained, containing metal-metal bonding (Mo-Ga, W-Ga) and/or low-valent metals (Mo(0/I), W(0/I), Ga(III)). Profound characterization of structure and bonding is performed (including TEM, XRD, FT-IR, DFT, MS, and ESR). Tb(0)/V(0) nanoparticles, in general, offer high potential for reactions/compounds different from the bulk lanthanide/transition metals and, specifically, for obtaining metal-metal bonding and low-valent metal compounds via a novel redox approach.