Bi₇^3–: The Missing Family Member, Finally Isolated and Characterized

Abstract

The synthesis and structure of Bi(7)(3-), the only missing member of the family of heptanuclear pnictogen cluster anions Pn(7)(3-) (Pn = pnictogen, a group 15 element excluding the unique nitrogen), is reported. The new species is synthesized by oxidation of a solution of K(5)Bi(4) by the solvent pyridine in the presence of (C(6)H(6))Cr(CO)(3). The existence of the species in solution is confirmed by electrospray mass spectrometry, while its structure is elucidated by single-crystal X-ray diffraction in the compound [K(2,2,2-crypt)](3)Bi(7)·2py (monoclinic, P2(1)/n, a = 13.8739(13) Å, b = 24.878(2) Å, c = 26.401(2) Å, β = 96.353(4)°, V = 9056.5(14) Å(3), Z = 4, and R1/wR2 = 0.0636/0.1390 for the observed data and 0.0901/0.1541 for all data).

[SnBi3]5− – ein Carbonat‐Analogon aus Metallatomen

“…als planarer Vierring; [12] ebenso konnte [Bi 2 ] 2À [10] aus einer Lçsung von K 3 Bi 2 gewonnen werden. Als weiteres Bi-Polyanion bildet sich [Bi 7 ] 3À aus K 5 Bi 4 in Pyridin in Anwesenheit von (C 6 H 6 )Cr(CO) 3 , [13] wohingegen das [Bi 11 ] 3À -Anion bisher nicht über eine direkte Route ausgehend von elementarem Bi oder einem ausschließlich Bi enthaltenden Polyanion gewonnen werden konnte,s ondern erst kürzlich als Zersetzungssprodukt des [GaBi 3 ] 2À -Ions aus Pyridin erhalten wurde. [14] Reaktionen der oben genannten Bismutide mit organometallischen Verbindungen führen zu einer Vielzahl heteratomarer Cluster,d ie nicht zwangsläufig die ursprünglichen Strukturmotive enthalten.…”

Chemical Bonding and σ-Aromaticity in Charged Molecular Alloys: [Pd2As14]4− and [Au2Sb14]4− Clusters

“…Anions with low nuclearities such as Sb n n − ( n  = 3, 5) and Bi n 3− ( n  = 2, 3) were isolated or stabilized by transition metals, suggesting the existence of [E n ] n − in solutions 16–18 . For higher nuclearities, Bi n 3− ( n =  7, 11) were obtained in the presence of Cr and Ga, respectively 19, 20 .…”

Solvate‐Induced Semiconductor to Metal Transition: Flat [Bi1−] Zigzag Chains in Metallic KBi⋅NH3 versus [Bi1−] Helices in Semiconducting KBi

“…Later, the dimer [Bi 2 ] 2À [12] was obtained from solutions of K 3 Bi 2 . Other established pnictides such as the polycyclic cages [Pn 7 ] 3À and [Pn 11 ] 3À (Pn = P, As, Sb) [6,16] followed a few years later; whereas [Bi 7 ] 3À was obtained from a solution of K 5 Bi 4 in pyridine, [17] the [Bi 11 ] 3À ion was not accessible by a direct route from an exclusively Bi-containing solid, but was formed upon the decomposition of [GaBi 3 ] 2À in pyridine. [18a] Whereas polybismuthide anions appear in rather complex polyanions, such as [(Bi 6 )Zn 3 (TlBi 5 )] 4À as ligands, [18b] bare Bi anions are less frequent.…”