Extracting [Pd@Sn₉]^4– and [Rh@Pb₉]^4– Clusters from their Binary Alloys Using “Metal Scissors”

Abstract

The search for novel ternary intermetallic compounds with specific structures is still a challenge. We found that the two-step synthesis giving a typical alloy in the first step followed by the reaction of this alloy with alkali metals is a promising route. The intermetallic compounds K 12 Pd 0.47 Sn 17 and K 4 RhPb 9 were synthesized by hightemperature reactions of preformed Pd-Sn and Rh-Pb alloys with K acting as "metal scissors" and were characterized by means of single crystal and powder X-ray diffractometry. The salt-like ternary phases K 12 Pd 0.47 Sn 17 and K 4 RhPb 9 contain novel endohedrally filled intermetalloid clusters [Pd@Sn 9 ] 4and [Rh@Pb 9 ] 4-, respectively. The crystal packing of the products corresponds to filled variants of the binary

Dimetalloylene (M‐E‐M) Complexes of Heavier Main Group Elements Ge, Sn, Pb, Bi via Cleavage of E‐X Bonds (X=N(SiMe3)2, OtBu) with an Iridium Hydride

“…Binary solid-state materials with transition metal-main group compositions (M x E y ) have properties that give them unique roles in various applications. [1][2][3][4][5][6][7] Quintessential examples are transition-metal silicides (e. g., M x Si y ), which are integral components in microelectronics [8] and serve as catalysts for important chemical transformations of silicon-containing materials. [9] In the latter context, the surface chemistry of the silicide promotes transformations that involve making or breaking bonds to the silicon center of key intermediates.…”

“…Binary solid‐state materials with transition metal‐main group compositions (M x E y ) have properties that give them unique roles in various applications [1–7] . Quintessential examples are transition‐metal silicides (e. g., M x Si y ), which are integral components in microelectronics [8] and serve as catalysts for important chemical transformations of silicon‐containing materials [9] .…”

K7In4As6 and K3InAs2 ‐ Two more Zintl phases showing the rich variety of In‐As polyanion structures

“…With the highest amount of alkali metals, isolated trigonal fragments [ TrPn 3 ] 6− such as [InAs 3 ] 6−[4] and associated dimers, trimers or condensed five‐membered rings such as [Ga 2 P 4 ] 6− , [5] [Ga 3 As 6 ] 9− , [6] and −[Ga 2 As 3 ]− [7] occur on one hand, or discrete tetrahedral [ TrPn 4 ] 9− units [8] such as [AlP 4 ] 9−[8a] as well as related dimers, linear or two‐ and three‐dimensional polymers occur on the other hand. Notice, that in case of the basic unit [ TrPn 3 ] 6− mesomeric forms with Tr‐Pn double bonds support the planarity of the [ TrPn 3 ] unit, and such units are even found among the heavier homologues of the Tr and Pn elements such as Ga and Bi, [9] which is in contrast to the well‐known ′double bond rule′ [10] . The [ TrPn 3 ] units might be interconnected in different ways by sharing edges, faces, corners, to build up three dimensional structures.…”

“…The [ TrPn 3 ] units might be interconnected in different ways by sharing edges, faces, corners, to build up three dimensional structures. Recently, K 10 Ga 3 Bi 6.65 has been reported containing linked trimers of [GaBi 3 ] units forming slightly deformed hexagonal [Ga 3 Bi 6 ] 9− polyanions with planar triangular‐coordinated Ga by Bi atoms beside isolated Bi−Bi dumbbells [9] . Among these structures, the nature of the anionic framework is collectively related to the number, the size, and the charge of the cations and, in turn, to the atomic ratio and thus the charge of the [ Tr x Pn y ] z− anion and its valence electron concentration.…”

Investigations on the Solubility of Sn4‐Cluster Compounds in Liquid Ammonia

“…[16] The role of organo-metallic reagents towards the solubility of A 4 Sn 4 phases was lately pointed out for Rb 4 Sn 4 . [17] Recently, we have investigated the appearance of intermetalloid clusters in solution, [18][19] and for the syntheses several intermetallic precursors have been studied. To open the synthetic potential of such intermetalloid clusters also experiments in solution are highly desired, and liquid ammonia is the first choice for such attempts.…”