Synthesis and X-Ray Crystallographic Characterisation of Frustum-Shaped Ligated [Cu H (DPPE) ] and [Cu H (DPPA) ] Nanoclusters and Studies on Their H Evolution Reactions.

We report new structural motifs for Cu nanoclusters that conceptually represent seed crystals for large face-centred cubic (FCC) crystal growth. Kinetically controlled syntheses, high resolution mass spectrometry experiments for determination of the dication formulae and crystallographic characterisation were carried out for [Cu H (DPPE) ][BF ][Cl] (DPPE=bis(diphenylphosphino)ethane) and [Cu H (DPPA) ][(BF ) ] (DPPA=bis(diphenylphosphino)amine) polyhydrido nanoclusters, which feature the unprecedented bifrustum and frustum metal-core architecture in metal nanoclusters. The Cu nanocluster contains two Cu frustum cupolae and the Cu nanocluster has one Cu frustum cupola and a Cu distorted hexagonal-shape base. Gas-phase experiments revealed that both Cu H and Cu H cores can spontaneously release H upon removal of one bisphosphine capping ligand.