Reactivities of Interstitial Hydrides in a Cu₁₁ Template: En Route to Bimetallic Clusters

Abstract

In sharp contrast to surface hydrides,r eactivities of interstitial hydrides are difficult to explore.W hen treated with am etal ion (Cu + ,A g + ,a nd Au + ), the stable Cu I dihydride template [Cu 11 H 2 {S 2 P(O i Pr) 2 } 6 (C CPh) 3 ]( H 2 Cu 11 )g enerates surprisingly three very different compounds,n amely [CuH 2 Cu 11 {S 2 P(O i Pr) 2 } 6 (C CPh) 3 ] + (1), [AgH 2 Cu 14 {S 2 P-(O i Pr) 2 } 6 ((CCPh) 6 ] + (2), and [AuCu 11 {S 2 P(O i Pr) 2 } 6 (C CPh) 3 Cl] (3). Compounds 1 and 2 are both M I species and maintain the same number of hydride ligands as their H 2 Cu 11 precursor.Neutron diffraction revealed the first time atrigonalpyramidal hydride coordination mode in the AgCu 3 environment of 2. 3 has no hydride and exhibits am ixed-valent [AuCu 11 ] 10+ metal core,m aking it at wo-electron superatom.

Hydride-Containing Eight-Electron Pt/Ag Superatoms: Structure, Bonding, and Multi-NMR Studies

“…Compounds 1 and 2 were investigated by DFT calculations at the BP86/Def2-TZVP level of calculations (see Computational Details in the Supporting Information). For the sake of computational limitations, the dtp and dsep ligands were replaced by S 2 PH 2 and Se 2 PH 2 models, respectively, a simplification which has been proved to be reasonable in many past investigations. ,,,,,− For each ligand, both C 1 and C 3 structures were considered. The resulting computed models are labeled 1′ ( C 1 ), 1′ ( C 3 ), 2′ ( C 1 ), and 2′ ( C 3 ) in the following.…”

“…18−20 Examples are explicitly demonstrated on the two encapsulated hydrides of [Cu 11 H 2 (dtp) 6 (C 2 Ph) 3 ]. 20,21 In addition, an interstitial hydride connected to noble metals, whose electronegativity values are larger than that of H, can behave as a "metallic" hydrogen. 8−13 Tsukuda and co-workers reported that the hydride dopant in (PdH@Au 10 ) 3+ contributes to the cluster eight-electron count, (1S) 2 (1P) 6 .…”

“…Upon reacting with Lewis acids such as salts of group 11 metals, interstitial hydrides can behave as 2-electron ligands to establish donor–acceptor relationships. − Examples are explicitly demonstrated on the two encapsulated hydrides of [Cu 11 H 2 (dtp) 6 (C 2 Ph) 3 ]. , In addition, an interstitial hydride connected to noble metals, whose electronegativity values are larger than that of H, can behave as a “metallic” hydrogen. − Tsukuda and co-workers reported that the hydride dopant in (PdH@Au 10 ) 3+ contributes to the cluster eight-electron count, (1S) 2 (1P) 6 . Sim and Lee put forward to a concept of superatom-in-superatom , in which the hydride dopant in [RhH@Ag 24 (SPhMe 2 ) 18 ] 2– NC provides one electron to the Rh atom, an open d-shell ([Kr]­4d 8 5s 1 ), to form a RhH “ superatom ” corresponding to a closed shell ([Kr]­4d 10 ) .…”

Interstitial Hydrides in Nanoclusters can Reduce M(I) (M=Cu, Ag, Au) to M(0) and Form Stable Superatoms

“…For M=Cu or Ag, the hydrides behave as regular 2-electron ligands, but for M=Au, they behave as electron donors, leading to the formation of a 2-electron superatom, with liberation of H 2 . [47] The neutron diffraction study proved that the trigonal pyramidal hydrides (μ 4 -H in AgCu…”

“…[46] 3 Cl], see Figure 2. [47] The Cu + and Ag + treated clusters remain both M(I) species and maintain the Werner E. van Zyl is Professor of Chemistry at the University of KwaZulu-Natal, South Africa. He received BScHons and MSc degrees in South Africa, and a PhD degree (1998) in inorganic chemistry from Texas A&M University, USA, followed by postdoctoral work (1999)(2000)(2001)(2002)(2003) same number of hydride ligands as the precursor, but the Au + treated cluster has no hydride and exhibits a mixed-valent [AuCu 11 ] 10 + metal core, making it a 2-electron superatom.…”