Nobel‐Metal Centered Polycations [Au@Bi₁₀]⁵⁺ or [Pd@Bi₁₀]⁴⁺ Embedded in Halogenido‐Bismuthate(III)‐Stannate(II) Frameworks

Abstract

The metal-rich halogenides AuBi 14Ϫδ Sn 2ϩδ X 21Ϫδ (δ ഠ 0.4) and PdBi 15Ϫδ Sn 1ϩδ X 21Ϫδ (δ ഠ 0.6) with X ϭ Cl, Br were crystallized from melts of the metals and BiX 3 . In the rhombohedral structures (space group R3; a ഠ 1050 pm; Ͱ ഠ 94°), noble-metal centered pentagonal antiprisms [Au@Bi 10 ] 5ϩ resp. [Pd@Bi 10 ] 4ϩ are embedded in halogenidometallate frameworks 3 ϱ [Bi 4Ϫδ Sn 2ϩδ X 21Ϫδ ] 5Ϫ resp. 3 ϱ [Bi 5Ϫδ Sn 1ϩδ X 21Ϫδ ] 4Ϫ . Mixed Bi III /Sn II site occupation allows the framework to adopt different charges. Further exchange of Bi III X 3 743against Sn II X 2 results in vacancies (δ) on the position of an isolated halide ion. In quantum chemical calculations the naked metal-clusters are found to be stable in D 5d symmetry with interatomic distances close to the observed ones. The significance of interactions between the Wade-type host cluster Bi 10 4ϩ and the closed-subshell guest atoms Au ϩ or Pd 0 is reflected in the molecular orbital diagram, the population analyses and the ELI-D.

Polyhedral Bismuth Polycations Coordinating Gold(I) with Varied Hapticity in a Homoleptic Heavy‐Metal Cluster

“…In 2006, Fernandéz et al reported on weak attractive interactions between gold(I) and bismuth(III) over the interatomic distance of 372 pm inside a dinuclear complex . A few years later, our group presented the gold‐centered pentagonal antiprism [Au@Bi 10 ] 5+ (Figure ) and the molecular clusters [Bi 10 Au 2 ]( E Bi 3 X 9 ) 2 ( E = As, Sb, Bi; X = Cl, Br; Figure ) . Despite the short Au–Bi distances of ca.…”

The Low‐Valent Bismuth Sulfide Bromide Cu3Bi2S3Br2

“…Cu 3 Bi 2 S 3 Br 2 = (Cu I ) 6 (Bi II 2 )(Bi III ) 2 S 6 Br 4 is the first low‐valent (“reduced”) compound among the copper bismuth chalcogenide halogenides 4,8. With silver or gold, a small number of bismuth‐rich halogenides, such as Ag 3 Bi 14 Br 21 ,9 [Bi 10 (AuSbBi 3 Br 9 ) 2 ],10 or [Au@Bi 10 ][Bi 3.6 Sn 2.4 Br 20.6 ],11 are known, yet no chalcogen containing representative. On the other hand, oxidized species that include dichalcogenide dumbbells, e.g.…”

Coordination chemistry of homoatomic ligands of bismuth, selenium and tellurium

“…[Pd@Bi 10 ] 4+ (Fig. 2f) [54,56,64] as well as the isoelectronic and isostructural [Au@Bi 10 ] 5+ [56] can be regarded as electron precise arachno clusters with endohedral s 0 d 10 closed-shell atoms Pd or Au + . Hence, they are cationic analogues to filled fullerenes such as He@C 60 [65,66] and polyanions with endohedral atoms such as [Pt@Pb 12 ] 2- [67,68].…”