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 (TbCl$_3$, VCl$_3$) 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 [Cp$_2$MCl$_2$] and carbonyl precursors [M(CO)$_6$] (M = Mo, W). As a result, the novel compounds [BMIm][Cp$_2$Mo(GaCl$_3$)$_2$] 1), [BMIm][Cp$_2$W(GaCl$_3$)$_2$] 2), [Cp$_2$Mo{GaCl$_2$(THF)}$_2$] 3), [BMIm][Cp$_2$MoGa$_2$Cl$_5$] 4), [VO(H$_2$Cyclal)Mo(CO)$_4$] 5) and [VO(H$_2$Cyclal)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.