Pure gold cluster of 1:9:9:1:9:9:1 layered structure: a novel 39-metal-atom cluster [(Ph3P)14Au39Cl6]Cl2 with an interstitial gold atom in a hexagonal antiprismatic cage

1992 ◽  
Vol 114 (7) ◽  
pp. 2743-2745 ◽  
Author(s):  
Boon K. Teo ◽  
Xiaobo Shi ◽  
Hong Zhang
Keyword(s):  
Metal Atom ◽  
Layered Structure ◽  
Gold Cluster ◽  
Gold Atom ◽  
Pure Gold ◽  
Atom Cluster

The Crystal Structure of Cesium Dodecachlorotrirhenate-(III), a Compound with a New Type of Metal Atom Cluster

1963 ◽  
Vol 2 (6) ◽  
pp. 1166-1171 ◽  
Author(s):  
J. A. Bertrand ◽  
F. A. Cotton ◽  
W. A. Dollase
Keyword(s):  
Crystal Structure ◽  
Metal Atom ◽  
Atom Cluster ◽  
New Type

ChemInform Abstract: MIXED-METAL ATOM CLUSTER COMPOUND CONTAINING SILVER(I) AND PLATINUM(II)

1984 ◽  
Vol 15 (30) ◽  
Author(s):  
R. USON ◽  
J. FORNIES ◽  
M. TOMAS ◽  
F. A. COTTON ◽  
L. R. FALVELLO
Keyword(s):  
Metal Atom ◽  
Cluster Compound ◽  
Mixed Metal ◽  
Atom Cluster

scholarly journals Carbocations as Secondary Coordination Sphere Z-Type Ligands – Anion-Induced Au(I)/Au(III) Oxidation and Impact on Reactivity

2019 ◽  
Author(s):  
Lewis Wilkins ◽  
Francois Gabbai
Keyword(s):  
Metal Atom ◽  
Coordination Sphere ◽  
Weak Interactions ◽  
Gold Atom ◽  
Lewis Acidity ◽  
Secondary Coordination Sphere ◽  
Covalently Bound

We describe our efforts towards the design of phosphine-based ligands featuring an electrophilic carbocationic moiety positioned to enter the secondary coordination sphere of the phosphine-bound metal atom. Using simple synthetic protocols, we have been able to obtain and fully characterize the complexes [(<i>o</i>-Ph<sub>2</sub>P(C<sub>6</sub>H<sub>4</sub>)Acr)AuCl]<sup>+</sup> ([<b>3</b>]<sup>+</sup>, Acr = 9-<i>N</i>-methylacridinium) and [(<i>o</i>-Ph<sub>2</sub>P(C<sub>6</sub>H<sub>4</sub>)Xan)AuCl]<sup>+</sup> ([<b>4</b>]<sup>+</sup>, Xan = 9-xanthylium). While only weak interactions occur between the gold atom and the methylium centers of these complexes, the more Lewis acidic [<b>4</b>]<sup>+</sup> readily reacts with chloride to afford a trivalent phosphine gold dichloride derivative (<b>7</b>) in which the metal atom is covalently bound to the former methylium center. This anion-induced Au(I)/Au(III) oxidation is accompanied by a conversion of the Lewis acidic methylium center in [<b>4</b>]<sup>+</sup> into an X-type ligand in <b>7</b>. This transformation leads us to conclude that the methylium center acts as a latent Z-type ligand poised to increase the Lewis acidity of the gold center, a notion supported by the carbophilic reactivity of these complexes.

Some theoretical and structural aspects of gold cluster chemistry

1982 ◽  
Vol 308 (1501) ◽  
pp. 75-83 ◽  
Keyword(s):  
Gold Cluster ◽  
Effective Interaction ◽  
Gold Atom ◽  
Cluster Compounds ◽  
Molecular Orbital Calculations ◽  
Cluster Chemistry ◽  
Theoretical Concepts ◽  
Simplified Approach ◽  
Wide Range ◽  
Semi Empirical

The bonding in tertiary phosphine cluster compounds of gold is sufficiently straightforward to permit an effective interaction between theoretical concepts developed from semi-empirical molecular orbital calculations and synthetic and structural chemistry. At the simplest conceptual level the isolobal nature of the Au(PR 3 ) fragment and either the CH 3 or H radicals provides a basis for understanding the structures of a wide range of homonuclear and heteronuclear clusters, e.g. Os 3 (CO) 10 - H(AuPPh 3 ) and (OG) 5 VAu 3 (PPh 3 ) 3 . However, this simplified approach neglects some secondary gold-gold interactions between adjacent gold atoms, which arise from the availability of the higher-lying gold 6p orbitals. In low-nuclearity clusters tetrahedral fragments, which permit the effective formation of four-centre two electron bonds between the Au(PR 3 ) fragments, are preferred to larger deltahedra. In higher-nuclearity clusters the stabilities of the clusters depend on the presence of a central gold atom that provides strong radial gold-gold bonding. The relative importance of the radial and tangential components to the total bonding has been effectively demonstrated by a structural comparison of alternative Au 9 (PR 3 )3/8+ clusters. The predictive capability of the theoretical approach has been demonstrated by the synthesis and structural characterization of the icosahedral cluster [Au 13 Cl 2 (PMe 2 Ph) 10 ]3+.

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