A combinatorial coordination-modulated approach to all-hydrocarbon-ligated intermetallic clusters.

The formation of Hume-Rothery-inspired intermetallic and all-hydrocarbon-ligated Ni/E clusters (E = Al, Ga) is studied. A library of organo-metallic complexes and small clusters is obtained when [Ni(cod) 2 ] is treated with ECp* in the presence of 3-hexyne (hex). While the alkyne reversibly coordinates side-on to the Ni/Ga species, it dimerizes at the Ni/Al species. The mass spectrometric monitoring of the reaction solutions provides insight into the chemical complexity generated by a combinatorial, coordination-modulated approach to control cluster nucleation and growth aiming at cluster size-focusing and selective synthesis of species such as [Ni 4 Ga 4 ](Cp*) 4 (hex) 2 .