Sc, Zr, Hf, and Mn Metal Nanoparticles: Reactive Starting Materials for Synthesis Near Room Temperature

Zerovalent scandium, zirconium, hafnium, and manganese nanoparticles are prepared by reduction of ScCl3, ZrCl4, HfCl4, and MnCl2 with lithium or sodium naphthalenide in a one-pot, liquid-phase synthesis. Small-sized monocrystalline nanoparticles are obtained with diameters of 2.4 +/- 0.2 nm (Sc), 4.0 +/- 0.9 nm (Zr), 8.0 +/- 3.9 nm (Hf) and 2.4 +/- 0.3 nm (Mn). Thereof, Zr(0) and Hf(0) nanoparticles with such size are shown for the first time. To probe the reactivity and reactions of the as-prepared Sc(0), Zr(0), Hf(0), and Mn(0) nanoparticles, they are exemplarily reacted in the liquid phase (e.g., THF, toluene, ionic liquids) with different sterically demanding, monodentate to multidentate ligands, mainly comprising O-H and N-H acidic alcohols and amines. These include isopropanol ((HOPr)-Pr-i), 1,1 '-bi-2-naphthol (H(2)binol), N,N '-bis(salicylidene)ethylenediamine (H(2)salen), 2-mercaptopyridine (2-Hmpy), 2,6-diisopropylaniline (H(2)dipa), carbazole (Hcz), triphenylphosphane (PPh3), N,N,N ',N '-tetramethylethylenediamine (tmeda), 2,2 '-bipyridine (bipy), N,N '-diphenylformamidine (Hdpfa), N,N '-(2,6-diisopropylphenyl)-2,4-pentanediimine ((dipp)(2)nacnacH), 2,2 '-dipydridylamine (Hdpa), and 2,6-bis(2-benzimidazolyl)pyridine (H(2)bbp). As a result, 22 new compounds are obtained, which frequently exhibit a metal center coordinated only by the sterically demanding ligand. Options and restrictions for the liquid-phase syntheses of novel coordination compounds using the oxidation of base-metal nanoparticles near room temperature are evaluated.