Making practical use of the pseudo-element concept: an efficient way to ternary intermetalloid clusters by an isoelectronic Pb−–Bi combination

Abstract

Syntheses of [K([2.2.2]crypt)](+) salts of binary Pb-Bi Zintl anions and their reaction with ZnPh(2) or Ni(cod)(2), yielding ternary intermetalloid Ni-Pb-Bi or Zn-Pb-Bi clusters, proved the use of binary precursors with fully isoelectronic atoms as an efficient and thus valuable synthetic approach to this class of clusters. (207)Pb NMR and ESI mass spectra provided insight into the solution behavior of the binary or ternary cages.

Intermetalloid Clusters: Molecules and Solids in a Dialogue

“…[50] Upon dissolution of K 2 Ge 2 P 2 ,beside the tetrahedral [Ge 2 P 2 ] 2À anion, also the nine-atomic [Ge 7 P 2 ] 2À unit is formed, which presumably originates from rearrangement processes in solution. [50] Upon dissolution of K 2 Ge 2 P 2 ,beside the tetrahedral [Ge 2 P 2 ] 2À anion, also the nine-atomic [Ge 7 P 2 ] 2À unit is formed, which presumably originates from rearrangement processes in solution.…”

“…[76] Whereas [TiCp 2 (h 1 -Sn 9 )(NH 3 )] 3À represents the product of as imple ligand exchange reaction of one NH 3 ligand by aS n 9 cluster,t he fragmentation of Sn 9 leads to [Ti(h 4 -Sn 8 )Cp] 3À ,inwhich aCpTifragment is capping ab asket-like Sn 8 cage.I naless defined reaction, the combination of fragmentation and aggregation leads to the complex anion [Ti 4 Sn 15 Cp 5 ] nÀ (n = 4or5)with abroad range of coordination modes between the Ti and Sn atoms,ranging from Cp 2 TiÀSn to CpTiÀSn and TiÀSn. [50,53] Ty pically,they undergo complete conversion to give new structural elements during their reactions.F or instance, in [Cd 3 (Ge 3 P) 3 ] 3À three [Ge 3 P] 3À tetrahedra are bridged via ac entral Cd triangle.E ven though the tetrahedral motif is retrieved, their original composition [Ge 2 P 2 ] 2À is not retained (Figure 11 a). Another remarkable fragmentation/aggregation sequence leads to [Ni 6 Ge 13 (CO) 5 ] 4À (Figure 8c), which is formed upon the reaction of K 4 Ge 9 with Ni(CO) 2 (PPh 3 ) 2 .T he product comprises two interpenetrating Ni/Ge icosahedra in which one vertex of each cluster simultaneously represents the central atom of the second icosahedron and thus one of the smallest possible molecular analogs of interpenetrating clusters as outlined for intermetallic compounds in the introduction.…”

Intermetalloide Cluster: Moleküle und Festkörper im Dialog

“…[50] Durch Auflçsung von "K 2 Ge 2 P 2 "w ird Abbildung 6. In den letzten Jahren wurden verschiedene Cluster,d ie aus Elementen aufgebaut sind, die durch Rçntgenbeugungsexperimente nicht unterscheidbar sind oder starke Fehlordnung der Atome aufweisen, mithilfe von Massenspektrometrie und quantenchemischen Rechnungen aufgeklärt.…”

“…Der experimentell nachgewiesene schrittweise Prozess beinhaltet hier den anfänglichen Anbau einer Ir(COD)-Einheit an die quadratische Fläche des Clusters,gefolgt von Fragmentierung und partieller Oxidation der resultierenden [Sn 9 Ir(COD)] 3À -Spezies zur endohedral gefüllten [Ir@Sn 12 ] 3À -Einheit. [50,53] [80] [Ni 2 @Sn 7 Bi 5 ] 3À , [81] [Ta@Ge 8 As 4 ] 3À ,[ Ta@Ge 6 As 4 ] 3À und [Ta@Ge 8 As 6 ] 3À ;d ie Bildung dieser Spezies erfordert jedoch komplizierte Umwandlungsschritte in Lçsung. [76] Während [TiCp 2 (h 1 -Sn 9 )(NH 3 4À .G e-Atomeblau, Au-Atome rot, Ge-Clusterg elb, Au 3 rot, Ge/Ni-Ikosaeder gelb und blau.…”

“…Vonden ternären Festkçrpern mit der nominellen Zusammensetzung "K 2 Tt 2 Pn 2 "( Tt = Te trelelement, Pn = Pentelelement) kann eine Vielzahl von [Tt 2 Pn 2 ] 2À -Tetraedern erhalten werden. [50] Durch Auflçsung von "K 2 Ge 2 P 2 "w ird Abbildung 6. Freisetzung von diskreten Clustern aus festen Precursorn:a)Extraktion von [Sn 9 ] 4À aus K 4 Sn 9 ,b)Extraktion von [CoSn 9 ] 5À aus K 5 CoSn 9 .Sn-Atome blau, Co-Atome rot, K-Atome grau, Sn-Cluster gelb.…”