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

Abstract 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 M Cl 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.