Synthesis and X‐Ray Crystallographic Characterisation of Frustum‐Shaped Ligated [Cu18H16(DPPE)6]2+ and [Cu16H14(DPPA)6]2+ Nanoclusters and Studies on Their H2 Evolution Reactions. Issue 9 (16th January 2018)

• Record Type: Journal Article
• Authors: Li, Jiaye; Ma, Howard Z.; Reid, Gavin E.; Edwards, Alison J.; Hong, Yuning; White, Jonathan M.; Mulder, Roger J.; O'Hair, Richard A. J.
• Is Part Of: Chemistry. Volume 24:Issue 9(2018)
• Page Start: 2070
• Page End: 2074
• Publication Date: 2018-01-16
• Subjects: coinage metal -- copper hydrides -- hydrogen release -- nanoclusters -- X-ray crystallography; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201705448
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: 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 [Cu18 H16 (DPPE)6 ][BF4 ][Cl] (DPPE=bis(diphenylphosphino)ethane) and [Cu16 H14 (DPPA)6 ][(BF4 )2 ] (DPPA=bis(diphenylphosphino)amine) polyhydrido nanoclusters, which feature the unprecedented bifrustum and frustum metal‐core architecture in metal nanoclusters. The Cu18 nanocluster contains two Cu9 frustum cupolae and the Cu16 nanocluster has one Cu9 frustum cupola and a Cu7 distorted hexagonal‐shape base. Gas‐phase experiments revealed that both Cu18 H16 and Cu16 H14 cores can spontaneously release H2 upon removal of one bisphosphine capping ligand. Abstract : Frustum‐shaped ligated nanoclusters : The reduction of Cu I precursors yielded the smallest triangular frustum‐shaped Cu polyhydrido nanoclusters, [Cu18 H16 (DPPE)6 ][BF4 ][Cl] and [Cu16 H14 (DPPA)6 ][(BF4 )2 ]. The Cu nanoclusters maintained their metal core after the complete hydride loss in the gas phase.