Diphosphine-Protected IrAu 12 Superatom with Open Site(s): Synthesis and Programmed Stepwise Assembly.

One or two phenylacetylide (PA) ligand(s) were successfully removed from the IrAu 12 superatomic core of [IrAu 12 (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 IrAu 12 core of [IrAu 12 (dppe) 5 (PA) 1 ] 2+ and [IrAu 12 (dppe) 5 ] 3+ with the remaining structure intact. Isocyanide was efficiently trapped at the open electrophilic site on [IrAu 12 (dppe) 5 (PA) 1 ] 2+ , whereas a dimer or trimer of the IrAu 12 superatoms was formed using diisocyanide as a linker. These results open the door to designed assembly of chemically modified metal superatoms.