Reactive Magnesium Nanoparticles to Perform Reactions in Suspension.

Zerovalent magnesium (Mg(0)) nanoparticles are prepared in the liquid phase (THF) by reduction of MgBr 2 either with lithium naphthalenide ([LiNaph]) or lithium biphenyl ([LiBP]). [LiBP]-driven reduction results in smaller Mg(0) nanoparticles (10.3±1.7 nm) than [LiNaph]-driven reduction (28.5±4 nm). The as-prepared Mg(0) nanoparticles are monocrystalline (d 101 =245±5 pm) for both types of reduction. Their reactivity is probed by liquid-phase reaction (THF, toluene) in suspension near room temperature (20-120 °C) with 1-bromoadamantane (AdBr), chlortriphenylsilane (Ph 3 SiCl), trichlorphenylsilane (PhSiCl 3 ), 9H-carbazole (Hcbz), 7-azaindole (Hai), 1,8-diaminonaphthalene (H 4 nda) and N,N'-bis(α-pyridyl)-2,6-diaminopyridine (H 2 tpda) as exemplary starting materials. The reactions result in the formation of 1,1'-biadamantane (1), [MgCl 2 (thf) 2 ]×Ph 6 Si 2 (2), [Mg 9 (thf) 14 Cl 18 ] (3), [Mg(cbz) 2 (thf) 3 ] (4), [Mg 4 O(ai) 6 ]×1.5 C 7 H 8 (5), [Mg 4 (H 2 nda) 4 (thf) 4 ] (6) and [Mg 3 (tpda) 3 ] (7) with 40-80 % yield. 1 and 2 show the reactivity of Mg(0) nanoparticles for C-C and Si-Si coupling reactions with sterically demanding starting materials. 3-7 represent new coordination compounds using sterically demanding N-H-acidic amines as starting materials. The formation of multinuclear Mg 2+ complexes with multidentate ligands illustrates the potential of the oxidative approach to obtain novel compounds with Mg(0) nanoparticles in the liquid phase.