Cluster Growth: Some Representative Reactions. Crystal Structures of [Pt(H)(AgNO3)(AuPPh3)8](NO3) and [Pt(H)(AgNO3)2(AuPPh3)8](NO3)

Abstract

The reaction of [Pt(AuPPh3)8](N0 3 )2 with AgNC>3 under H2-atmosphere yields two new hydride-containing P t-A u -A g cluster compounds: [Pt(H)(AgN0 3 )(AuPPh3)8](N0 3 ) (1) and [Pt(H)(AgN03)2(AuPPh3)8](N03) (2). These reactions show intimate details on cluster growth: the nine-metal-atom particle [Pt(AuPPh3)8](N0 3)2 grows via oxidative addition of H2, deprotonation and electrophilic addition o f Ag+ to a 10-and then to an 11-metal-atom particle, 2. Cluster compounds 1 and 2 were characterized by elemental analyses, ICP analyses, IR and NM R ( lH, 3,P and ,95Pt) spectroscopy, and electrical conductivity measurements. The crystal and molecular structures of 1 and 2 have been determined by means of single-crystal X-ray analyses. The compound [Pt(H)(AgNC>3)- (AuPPh3)

Synthesis of Trimetallic (HPd@M2Au8)3+ Superatoms (M = Ag, Cu) via Hydride-Mediated Regioselective Doping to (Pd@Au8)2+

“…However, it is still a challenge to obtain the doped clusters with the desired composition in high yield due to the difference in the relative reduction rates of the precursor metal ions. To circumvent the difficulties, other methods such as galvanic and antigalvanic methods have been developed. ,,,,− Tri- and tetrametallic clusters have been synthesized by antigalvanic processes between preformed bimetallic clusters and heterometal complexes − and reduction of heterometal precursors in the presence of preformed bimetallic clusters. − …”

Hydride-Doped Gold Superatom (Au9H)2+: Synthesis, Structure, and Transformation

“…Steggerda et al reported a similar growth reaction of [PtAu 8 (PPh 3 ) 8 ] 2+ using H 2 under basic conditions. , First, [Pt­(H 2 )­Au 8 (PPh 3 ) 8 ] 2+ is produced by dissociative adsorption of H 2 on [PtAu 8 (PPh 3 ) 8 ] 2+ and a proton is subsequently abstracted from [Pt­(H 2 )­Au 8 (PPh 3 ) 8 ] 2+ by the base (such as pyridine) to form [Pt­(H)­Au 8 (PPh 3 ) 8 ] + . Finally, a coinage metal cation can be introduced to form [Pt­(H)­(X) n Au 8 (PPh 3 ) 8 ] + (X = Au + , Ag + , Cu + ; n = 1, 2).…”

Gold–Heterometal Interactions and Bonds

“…For most of them the metallic frameworks can be derived from a Pt-centered Au 12 icosahedron by removing seven [41], six [555,556], four [556,558], three [548,[559][560][561], or two [556] vertices. Clusters with similar cores in which up to three gold atoms are replaced by atoms of another metal have also been reported, for example, Pt-Au 5 Pt 2 [550], Pt-Au 6 Hg [42], Pt-Au 5 Hg 2 [41], Pt-Au 8 Ag [556,562,563], Pt-Au 8 Ag 2 [563], Pt-Au 8 Cu [556,564] and Pt-Au 8 Cu 2 [564]. In another few compounds additional metal atoms are connected to an M 3 face of trimetallic frameworks derived from Pt-centered icosahedra, for example, Cu(Pt-Au 6 Cu 3 ) [565] and Ag 2 (Pt-Au 6 Recently, the first nanosized Au/Pt cluster, [(Ph 3 P) 2 Au 2 ] 2 Pt 13 (CO) 10 (PPh 3 ) 4 411, was reported; it contains a Pt-centered Pt 12 icosahedral cage capped by two (Ph 3 P)AuAu(PPh 3 ) units [567].…”