Synthesis of Bimetallic Copper‐Rich Nanoclusters Encapsulating a Linear Palladium Dihydride Unit

Abstract

The structurally precise Cu‐rich hydride nanoclusters [PdCu14H2(dtc/dtp)6(C≡CPh)6] (dtc: di‐butyldithiocarbamate (1); dtp: di‐isopropyl dithiophosphate (2)) were synthesized from the reaction of polyhydrido copper clusters [Cu28H15(S2CNnBu2)12]+ or [Cu20H11{S2P(OiPr)2}9] with phenyl acetylene in the presence of Pd(PPh3)2Cl2. Their structures and compositions were determined by single‐crystal X‐ray diffraction and the results supported by ESI‐mass spectrometry. Hydride positions in 1 were confirmed by single‐crystal neutron diffraction. Each hydride is connected to one Pd0 and four CuI atoms in slightly distorted trigonalbipyramidal geometry. The anatomies of clusters 1 and 2 are very similar and DFT calculations allow rationalizing the interactions between the encapsulated [PdH2]2− unit and its Cu14 bicapped icosahedral cage. As a result, Pd has the highest coordination number (14) so far recorded.

Polyhydrido Copper Nanoclusters with a Hollow Icosahedral Core: [Cu30H18{E2P(OR)2}12] (E=S or Se; R=nPr, iPr or iBu)

“…In addition, two hydrides bondedt o Pd are embodied in the icosahedron.T he metallic frameworks of 4 and 5 have idealized D 3d symmetry,w here the C 3 passes throught he two capping Cu atoms, the two hydrides and the central Pd atom. Their overall geometry is similartoour recently reported cluster [PdH 2 Cu 14 {S 2 P(OiPr) 2 } 6 (CCPh) 6 ] [75] (Figure 7a-c). One of the noteworthy features in 4 and 5 is that the central Pd 0 atom is connected to the two hydrides and twelveC ua toms,t hus reaching ac oordination number of 14, the highest so far documented.…”

“…Very recently,w er eported the first and still unique structurally-precise CuÀM( M = group 10 element) bimetallic NC, namely [PdH 2 Cu 14 {S 2 P(OiPr) 2 } 6 (CCPh) 6 ]. [75] It was synthesized by the reaction of ap olyhydrido copper cluster ([Cu 20 H 11 {S 2 P(OiPr) 2 } 9 ]o r [Cu 32 H 20 {S 2 P(OiPr) 2 } 12 ]) with Pd II in the presence of alkynes. We were thus tempted to react 1 H with Pd II in the presence of phenyla cetylene as an auxiliary ligand.T he reactionl eads to the isolation of the new cluster [PdH 2 Cu 14 {S 2 P(OnPr) 2 } 6 (CCPh) 6 ] (4)( Scheme 1).…”

“…Unsurprisingly,D FT calculations indicatet hat 4 and 5 have the same electronic structure as their isostructuralr elative [PdH 2 Cu 14 {S 2 P(OiPr) 2 } 6 (CCPh) 6 ]. [75] They can be described as made of al inear 14-electron [PdH 2 ] 2À complex encapsulatedi n ab icapped icosahedron made of 14 Cu I centers, the resulting [(PdH 2 )@Cu 14 ] 12 + core being furthers tabilized by 6d tp and 6 alkynyl anionic ligands.…”

Mono- and hexa-palladium doped silver nanoclusters stabilized by dithiolates

“…18 As a part of research on heavy atom doping on Ag and Cu NCs, we have recently produced structurally precise alloy NCs [AuAg19{S2P(O n Pr)2}12], 19 [AuAg20{Se2P(OEt)2}12] +20 and [PdCu14H2{S2CN n Bu2/S2P(O i Pr)2}6(C≡CPh)6]. 21 in this study we isolated two unprecedented 21 and 20 metal based Pd doped Ag NCs [PdAg20{S2P(O n Pr)2}12] (1) and [Pd6Ag14(S){S2P(O n Pr)2}12] (2), respectively. The results provide that the cluster 2 is the first evidence of multi palladium doped Ag NC characterized by single-crystal X-ray diffraction study.…”

The emergence of mass spectrometry for characterizing nanomaterials. Atomically precise nanoclusters and beyond

“…51 Usually, the composition, size, and monodispersity can be determined by high resolution mass spectrometry for atomically precise nanoclusters, in addition with other characterization techniques (usually NMR, FT-IR, X-ray absorption and photoelectron spectroscopies), and this was done mostly for nanoclusters containing gold or silver. HRMS was also applied for characterizing atomically monodisperse copper, [80][81][82][83][84][85][86] nickel, [87][88][89] cobalt, 90 palladium 91 nanoclusters and molecule-like CdSe nanoclusters. 92 In order to better tune chemical/physical properties of atomically precise metal nanoclusters, several strategies have been adopted in particular using either ligand engineering or metallic kernel (or core) alloying.…”