[Ru(Bi8)2]6+ - A cluster in a highly disordered crystal structure is the key to the understanding of the coordination chemistry of bismuth polycations

Publikation: Beitrag in FachzeitschriftForschungsartikelBeigetragenBegutachtung

Beitragende

Abstract

Black platelets of Bi39.67(7)Ru2Br35.0(2) were crystallized from a melt of Bi, BiBr3, and Ru. In the tetragonal crystal structure [P4/mbm, a = 1311.92(6) pm, c = 3018.2(4) pm at 155(5) K], cluster cations [(Bi82+)Ru2+(Bi 82+)] are embedded in a matrix of disordered bromido-bismuthate(III) groups. A thorough analysis of the disorder in the anionic part enabled the unambiguous assignment of the cluster charge. The η4-coordination of the two Bi82+ square antiprisms to the RuII atom in the sandwich complex resembles the bonding of Bi5+ and Bi82+ in the clusters [(Bi5+)Ru+(Bi4Br 4)Ru+(Bi5+)] and [(Bi 82+)Ru+(Bi4Br4)Ru +(Bi5+)] as well as of Bi4 2- in1∞[(Bi42-)Ru+(Bi 4Br4)Ru+]. By combining crystal chemical considerations for all mentioned compounds and using quantum chemical calculations, a common bonding scheme for the coordination compounds of bismuth polycations and polyanions was established. The η4-coordinating bismuth polycations and polyanions act as six electron donors, comparable to nido-carborane ligands, Zintl anions E94- and E 56- (E = Si to Pb), cyclopentadienyl ligands, or the cyclobutadiene dianion. The electron count for the transition metal is 18 in all finite clusters.

Details

OriginalspracheEnglisch
Seiten (von - bis)2401-2405
Seitenumfang5
FachzeitschriftZeitschrift fur Anorganische und Allgemeine Chemie
Jahrgang639
Ausgabenummer14
PublikationsstatusVeröffentlicht - Nov. 2013
Peer-Review-StatusJa

Externe IDs

ORCID /0000-0002-2391-6025/work/159171923

Schlagworte

ASJC Scopus Sachgebiete

Schlagwörter

  • Bismuth, Cluster compounds, Polycations, Ruthenium, Sandwich complexes