Sb₈(GaCl₄)₂: Isolation of a Homopolyatomic Antimony Cation

Abstract

An almost perfect square‐antiprismatic geometry is observed for Sb82+ (see picture), as predicted by the Wade rules. The title compound, which was synthesized in benzene at room temperature, represents the first homopolyatomic antimony cation and has SbSb bond lengths of 285–300 pm.

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

“…[296] More general homopolyatomic clusters are well-established for post-transition-metal elements,h owever,m any of these species are anionic. [330] Thec rystal structure shows arachno-[Sb 8 ] 2+ dications with as quare-antiprismatic geometry,a sp redicted by Wades rules,a nd consistent with the bismuth species [Bi 8 ][AlCl 4 ] 2 , which also possesses square-antiprismatic geometry. [1,329] In addition, only the dicationic antimony species [Sb 8 ] 2+ supported by the [GaCl 4 ] À anion has been reported.…”

“…With the exception of the well-known bismuth cations,G roup 15 homopolyatomic cations are particularly rare. [330] For phosphorus,[NO][Al(OR F ) 4 ]was used for the oxidation of P 4 to [P 9 ] + via [P 4 NO] + .T he structure,d etermined by NMR spectroscopy,consists of two P 5 cages linked by aphosphonium atom to give a D 2d -symmetric Zintl cluster ( Figure 9). [330] Thec rystal structure shows arachno-[Sb 8 ] 2+ dications with as quare-antiprismatic geometry,a sp redicted by Wades rules,a nd consistent with the bismuth species [Bi 8 ][AlCl 4 ] 2 , which also possesses square-antiprismatic geometry.…”

Structural Investigation of a Fully Ordered closo‐Ge92– Cluster in the Compound [K+(2,2,2‐crypt)]2Ge92–

“…However, we do not want to point the finger since we have certainly made such a mistake ourselves in the past (a proposed Sb 5 3+ cluster was later shown to be Sb 8 2+ ). [21,22] An additional challenge is that even if the composition and structure are correct, they cannot be unambiguously rationalised in terms of electron bookkeeping rules, [23] because the structural fluxionality of the clusters is too high. The present work, employing a detailed structural analysis of highquality crystals obtained from organic solutions at low tem-perature, is to attempt to iron out some of the ambiguities mentioned above.…”

The First Step of the Oxidation of Elemental Sulfur: Crystal Structure of the Homopolyatomic Sulfur Radical Cation [S8].+

“…[1] Lately,t he synthetic strategies and methods that were very successful in the past did not allow for further progress.Nevertheless,byusing new methods and techniques,s pectacular results were still obtained even recently.F or instance,e vidence for the first homopolyatomic phosphorus cation [P 9 ] + was obtained by using modern weakly coordinating anions instead of classical hexafluorometallates such as [AsF 6 ] À . [3] Recently,i onic liquids as reaction media [4] and electrochemical syntheses [5] were introduced as new strategies for the field of homopolyatomic cations of the heavier chalcogen elements. [3] Recently,i onic liquids as reaction media [4] and electrochemical syntheses [5] were introduced as new strategies for the field of homopolyatomic cations of the heavier chalcogen elements.…”