The Subtle Influence of Binary versus Homoatomic Zintl Ions: The Phenyl‐Ligated Trimetallic Cage [Sn₂Sb₅(ZnPh)₂]³⁻

Abstract

One decade after the first characterization of Zintl ions by Kummer and Diehl [1a] and Corbett, [1b, c]

Synthesis and Characterization of [Rb([18]crown‐6)]3As15Zn·4NH3 and [Rb([2.2.2]crypt)]4Sb14Zn·8NH3

“…Knowing that the electrons are fluctuating from the Zn1-As9 bond into the As13-As9 bond and further the LP-As13 one can easily understand that there is also fluctuation into the LP-As13 (0.1468) from the As13-As9 bond. Analogous observations can be made for the other [11,12] Formally, the positive charge is located on the Zn atom and six negative charges on the twofold bonded atoms of the two cages. 3 .…”

[Eu@Sn6Bi8]4−: A Mini‐Fullerane‐Type Zintl Anion Containing a Lanthanide Ion

“…The mass spectra reveal several [Sn x Bi y ] fragments (x + y = 3-9; see Supporting Information) to result from decomposition/re-arrangement of the starting compound [Sn 2 Bi 2 ] 2À , producing nine-atom cages as atom-consuming major side-products, which is common for this type of reaction. [11] One fragment of low intensity accords to the composition [Sn 3 Bi 4 ] À (Figure 5 a) [15] DFT calculations of [Sn 3 Bi 4 ] 6À resulted in convergence for all 10 possible isomers (see Supporting Information), with the lowest-energy isomer ( Figure 5 b) representing exactly the topology of a hemisphere of the lowest-energy structure of the cluster (conformer I in Figure 4). This fragment, together with its low abundance, might give a hint for the growing pathway of the observed, low-yield enneahedron in 1, out of two seven-atom hemispheres.…”

[Eu@Sn6Bi8]4−: Ein Mini‐Fulleran‐artiges Zintl‐Anion mit interstitiellem Lanthanoidion

“…[11,15] [11,12] ). Dieses Ergebnis bestätigt eindeutig einen Spingrundzustand in 1, der größer ist als S = 5/2 (erwartete Curie-Konstante für S = 5/2: 4.375 cm 3 K mol À1 ), und schließt definitiv einen Grundzustand mit S = 1/2 aus.…”