Structure and properties of the hydride-containing cluster ion hydrido(triphenylphosphine)heptakis[(triphenylphosphine)gold]platinum(2+)

Abstract

The title cluster ion can be prepared by the reaction of Hz with Au(PPh,)+ and Pt(PPh,), as well as by the reaction of Pt-(AuPPh3)82+ with PPh3 and an acid. Mossbauer spectra show that the central atom is Pt. The structure was determined by X-ray diffraction of P~(H)(PP~,)(AUPP~~)~(PF~)~.~/~CH~CI~ (triclinic, Pi, a = 17.085 (6) A, b = 17.301 (8) A, c = 29.401 (12) A, a = 94.62 (IO)', 0 = 96.26 (S)', y = 118.24 ( 5 ) O , V = 7523.2 A', Z = 2, R = 0.085 and R , = 0.1 15 for 15 921 unique reflectionsand 596 variables, Cu K a radiation). In the metal cluster the central Pt is surrounded by seven Au atoms and one PPh3 in a distorted cubic geometry, each Au being attached to a PPh,. The H is close to Pt and at least two Au atoms, as can be concluded from deformations in the metal frame and from Orpen calculations. Detailed ,'P, 19sPt, and IH NMR spectra are presented. The different Au-PPh, sites, present in the crystal, are equilibrated in solution at room temperature.

Hydride-Mediated Controlled Growth of a Bimetallic (Pd@Au8)2+ Superatom to a Hydride-Doped (HPd@Au10)3+ Superatom

“…This growth process can be viewed as the transformation of an oblate (Au 9 ) 3+ superatom with an electron configuration of (1S) 2 (1P) (ref ) to a spherical (Au 11 ) 3+ superatom with a closed electron configuration of (1S) 2 (1P) (ref ) via a hydride-doped superatom of (HAu 9 ) 2+ . Hydride-mediated core growth to [PtAu 8 (PPh 3 ) 8 ] 2+ has also been reported in a Pt–Au bimetallic cluster [HPtAu 7 (PPh 3 ) 8 ] 2+ . These observations suggest that the addition of Au atoms to the seed clusters is initiated by electron donation via H – adsorption followed by the replacement of H + with Au + species rather than direct adsorption of the reduced Au(0) species.…”

“…Hydride-mediated core growth to [PtAu 8 (PPh 3 ) 8 ] 2+ has also been reported in a Pt−Au bimetallic cluster [HPtAu 7 (PPh 3 ) 8 ] 2+ . 12 These observations suggest that the addition of Au atoms to the seed clusters is initiated by electron donation via H − adsorption followed by the replacement of H + with Au + species rather than direct adsorption of the reduced Au(0) species. Hydride affects not only the chemical properties of the clusters toward the controlled growth but also the geometric and electronic structures of the clusters.…”

Atomically Precise Colloidal Metal Nanoclusters and Nanoparticles: Fundamentals and Opportunities

“…Phosphine-protected gold nanoclusters can also form a series of Au–Ag bimetal nanoclusters, as reported in early works by the Teo group. − ,, A unique cluster-of-clusters growth mode was identified by Teo et al (Figure ), in which the 13-atom icosahedron serves as the building block and vertex sharing gives rise to biicosahedral and cyclic triicosahedral structures (Figure ). Mingos and Pignolet and co-workers − also reported a number of gold-based bimetal clusters protected by phosphine in the 1980–1990s.…”

Gold–Heterometal Interactions and Bonds

“…Alternatively, it might be described as derived from a distorted Pt-centered Au 8 cube with two missing vertices. A similar metallic framework, that is, Pt-centered Au 8 cube with one missing vertex, was found in the related [{(Ph 3 P) Au} 7 Pt(H)(PPh 3 )](PF 6 ) 2 408 [554]. Trimetallic Hg-Au-Pt clusters based on a Ptcentered Au 8 square antiprism were also reported (see Section 2.2) [41][42][43][44].…”