Reiß Andreas, Appenzeller Anja, Baur Jule J, Wenzel Jonas O, Popescu Radian, Beuthert Kathrin, Dehnen Stefanie, Eggeler Yolita M, Breher Frank, Klopper Wim, Feldmann Claus
Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstrasse 15, D-76131, Karlsruhe, Germany.
Institute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 2, D-76131, Karlsruhe, Germany.
Small. 2025 Aug;21(31):e2503498. doi: 10.1002/smll.202503498. Epub 2025 Jun 9.
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, VCl) 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 [CpMCl] and carbonyl precursors [M(CO)] (M = Mo, W). As a result, the novel compounds [BMIm][CpMo(GaCl)] 1), [BMIm][CpW(GaCl)] 2), [CpMo{GaCl(THF)}] 3), [BMIm][CpMoGaCl] 4), [VO(HCyclal)Mo(CO)] 5) and [VO(HCyclal)W(CO)] 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.
镧系金属和早期过渡金属——尽管原则上具有高反应活性——但由于表面积小、溶解度低和/或钝化作用，仅表现出有限的反应活性。在这方面，小尺寸金属纳米颗粒能够为室温下的液相反应提供机会。通过铽金属纳米颗粒（2.8±0.4纳米）和钒金属纳米颗粒（1.2±0.2纳米），展示了具有不同反应活性的代表性镧系金属和早期过渡金属。两者均通过在四氢呋喃中还原简单前驱体（TbCl、VCl）制备而成。Tb(0)/V(0)纳米颗粒具有高反应活性，并用作液相（四氢呋喃、甲苯、正十二烷、离子液体）中的起始原料，以与环戊二烯基前驱体[CpMCl]和羰基前驱体[M(CO)]（M = Mo、W）进行反应。结果，获得了新型化合物[BMIm][CpMo(GaCl)] 1)、[BMIm][CpW(GaCl)] 2)、[CpMo{GaCl(THF)}] 3)、[BMIm][CpMoGaCl] 4)、[VO(HCyclal)Mo(CO)] 5)和[VO(HCyclal)W(CO)] 6)，它们含有金属-金属键（Mo-Ga、W-Ga）和/或低价金属（Mo(0/I)、W(0/I)、Ga(III)）。对结构和键合进行了深入表征（包括透射电子显微镜、X射线衍射、傅里叶变换红外光谱、密度泛函理论、质谱和电子自旋共振）。一般来说，Tb(0)/V(0)纳米颗粒在与块状镧系/过渡金属不同的反应/化合物方面具有很大潜力，特别是通过一种新型氧化还原方法获得金属-金属键和低价金属化合物。
