The intermetalloid cluster [(Cp*AlCu)6H4], embedding a Cu6 core inside an octahedral Al6 shell: molecular models of Hume-Rothery nanophases.

Defined molecular models for the surface chemistry of Hume-Rothery nanophases related to catalysis are very rare. The Al-Cu intermetalloid cluster [(Cp*AlCu)6H4] was selectively obtained from the clean reaction of [(Cp*Al)4] and [(Ph3PCuH)6]. The stronger affinity of Cp*Al towards Cu sweeps the phosphine ligands from the copper hydride precursor and furnishes an octahedral Al6 cage to encapsulate the Cu6 core. The resulting hydrido cluster M12H4 reacts with benzonitrile to give the stoichiometric hydrometalation product [(Cp*AlCu)6H3(N=CHPh)].

Colloidal nickel/gallium nanoalloys obtained from organometallic precursors in conventional organic solvents and in ionic liquids: noble-metal-free alkyne semihydrogenation catalysts.

Efforts to replace noble-metal catalysts by low-cost alternatives are of constant interest. The organometallic, non-aqueous wet-chemical synthesis of various hitherto unknown nanocrystalline Ni/Ga intermetallic materials and the use of NiGa for the selective semihydrogenation of alkynes to alkenes are reported. Thermal co-hydrogenolysis of the all-hydrocarbon precursors [Ni(COD)2] (COD = 1,5-cyclooctadiene) and GaCp* (Cp* = pentamethylcyclopentadienyl) in high-boiling organic solvents mesitylene and n-decane in molar ratios of 1 : 1, 2 : 3 and 3 : 1 yields the nano-crystalline powder materials of the over-all compositions NiGa, Ni2Ga3 and Ni3Ga, respectively. Microwave induced co-pyrolysis of the same precursors without additional hydrogen in the ionic liquid [BMIm][BF4] (BMIm = 1-butyl-3-methyl-imidazolium) selectively yields the intermetallic phases NiGa and Ni3Ga from the respective 1 : 1 and 3 : 1 molar ratios of the precursors. The obtained materials are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), IR, powder X-ray diffraction (PXRD) and atomic absorption spectroscopy (AAS). The single-source precursor [Ni(GaCp*)(PMe3)3] with a fixed Ni : Ga stoichiometry of 1 : 1 was employed as well. In comparison with the co-hydrogenolytic dual precursor source approach it turned out to be less practical due to inefficient nickel incorporation caused by the parasitic formation of stable [Ni(PMe3)4]. The use of ionic liquid [BMIm][BF4] as a non-conventional solvent to control the reaction and stabilize the nanoparticles proved to be particularly advantageous and stable colloids of the nanoalloys NiGa and Ni3Ga were obtained. A phase-selective Ni/Ga colloid synthesis in conventional solvents and in the presence of surfactants such as hexadecylamine (HDA) was not feasible due to the undesired reactivity of HDA with GaCp* leading to inefficient gallium incorporation. Recyclable NiGa nanoparticles selectively semihydrogenate 1-octyne and diphenylacetylene (tolan) to 1-octene and diphenylethylene, respectively, with a yield of about 90% and selectivities of up to 94 and 87%. Ni-NPs yield alkanes with a selectivity of 97 or 78%, respectively, under the same conditions.