Synthesis and Structure of the Cluster [NaAu₁₂Se₈]³⁻: An Inorganic Cryptand Complex

Abstract

A cube with twelve linearly coordinated gold atoms in the middle of the edges and eight trigonally coordinated selenium atoms at the corners is found in the structure of the title compound 1 (see right). A sodium ion is encapsulated in the center of the cube and interacts with the gold atoms. The (Et4N) 3 salt of this inorganic cryptand complex is formed in the reaction of AuCN and Na2Se in the presence of Et4NCl.

[Cu13{S2CNnBu2}6(acetylide)4]+: A Two‐Electron Superatom

“…The central copper atom (Cu1) acts a template in the formation of this large cluster, and strongly binds to the twelve other Cu atoms. Whereas a couple of examples of Au 12 and Ag 12 dodecahedra that encapsulate a sodium or silver atom, respectively, are known, 2 is the first example of a copper cuboctahedron encapsulating another atom. It is noteworthy that no guest element is present in the dodecahedral structures of [Cu 12 S 8 ] 4− , [Cu 12 (NPh) 8 ] 4− , [( t Bu 3 SiP) 6 Cu 12 ], and [Cu 12 E 6 (PR 3 ) 8 ] (E=S, Se, Te) .…”

Laser Ablation Synthesis of Gold Selenides by using a Mass Spectrometer as a Synthesizer: Laser Desorption Ionization Time‐of‐Flight Mass Spectrometry

“…The structure of several gold and selenium clusters is known. [48,49] Aside from the aforementioned minerals, only af ew gold selenide structures have been described, [5,6,[16][17][18] and the structures of the most of the clusters generated in this work were not previously reported. Furthermore,t he number of conceivable isomers greatlye scalatesw ith the number of atoms.…”

“…[2] Gold polyselenidec omplexes,s uch as [Au 2 (Se 2 )(Se 3 )] 2À , [Au 2 (Se 2 )(Se 4 )] 2À ,[ Au 2 Se 2 (Se 4 ) 2 ] 2À or inorganic cryptate [NaAu 12 Se 8 ] 3À were also synthesized. [16][17][18] Interaction of selenium dihydridew ith smallg old clusters (Au n , n = 3, 4) yields Au n SeH 2 complexes with stable gold-seleniumbonds. [19] Reaction of gold trichloride with seleniumr educes gold(III) to elementalg old in solutions heatedn early to boiling point.…”

Gold: Inorganic & Coordination Chemistry

“…The volume of the sulfur cluster is 12% smaller than the selenium analog (98 vs 111Å 3 ), and, hence, the sodium anion cannot be included inside the cage. 26 This inorganic cryptand complex anion [NaAu 12 Se 8 ] 3− , (2), is prepared from a mixture of AuCN, Na 2 Se, and Et 4 NCl. …”

“…The structure of [Au 9 (Ptol 3 ) 8 ] 3+ can be derived from a centered icosahedron, but it is more simply pictured as a bicapped centered chair as shown in (25). The cluster [Au 9 (Ptol 3 ) 9 ](NO 3 ) 3 has been prepared by NaBH 4 reduction of [Au(Ptol) 3 (26) Another Au 9 cluster, [Au 9 (PCy 3 ) 5 (SCN) 3 ], was prepared by NaBH 4 reduction of [Au(PCy 3 )SCN], and this structure can also be described in terms of a centered icosahedron with different gold atoms missing or as bicapped centered chair as shown in (27). The reduction of [Au 9 (PPh 3 ) 8 ] 3+ gives [Au 9 (PPh 3 ) 8 ] + with a distorted centered cubane structure (28).…”