Diphosphine-Protected IrAu₁₂ Superatom with Open Site(s): Synthesis and Programmed Stepwise Assembly

One or two phenylacetylide (PA) ligand(s) were successfully removed from the IrAu₁₂ superatomic core of [IrAu₁₂(dppe)₅(PA)₂]⁺ (dppe=1,2-bis(diphenylphosphino)ethane) by reaction with controlled amounts of tetrafluoroboric acid. Optical and nuclear magnetic resonance spectroscopies and density functional theory calculations revealed the formation of open Au site(s) on the IrAu₁₂ core of [IrAu₁₂(dppe)₅(PA)₁]²⁺ and [IrAu₁₂(dppe)₅]³⁺ with the remaining structure intact. Isocyanide was efficiently trapped at the open electrophilic site on [IrAu₁₂(dppe)₅(PA)₁]²⁺, whereas a dimer or trimer of the IrAu₁₂ superatoms was formed using diisocyanide as a linker. These results open the door to designed assembly of chemically modified metal superatoms.