Evidence for the Existence of (SiP₆H₂)^2– and its Homologs as Examples of Binary Nortricyclane‐Type Zintl Anions

Abstract

The extraction of stoichiometric ternary K/Si/P, K/Ge/P, and K/Si/As solid mixtures with en/crypt-222 afforded compounds with binary anions of the respective groups 14/15 elemental combination. Although the analysis of the products turned out to be extremely difficult owing to their intrinsically poor crystallinity and low solubility, we have evidence that one of them contains (SiP 6 H 2 ) 2anions. Preliminary data from the two other compounds indicate the existence of the heavier Ge/P and Si/As variants as well. The combination of all analytical results, including X-ray crystallography, energy-dispersive X-ray * Prof. Dr. S. Dehnen

From a nanoparticular solid-state material to molecular organo-f-element-polyarsenides

“…Nevertheless, they are in a range observed for other potassium polyarsenides (e.g. 3.19-3.84 Å in [K(2.2.2-cryptand)] 2 (KAs 7 )) 39,40. Aer the successful application of the 3-electron reducing agents A(La) and A(Ce) in the activation of nanoscale arsenic, we felt challenged to treat As 0 nano with 4-electron reducing agents in the reduction process.…”

Synthesis and Characterization of Homoleptic Zintl Anions [(Pn7)M(Pn7)]4− (M/Pn=Pb/As, Zn/Bi)

“…Color code: Bi (blue), Zn (black), K (light turquoise). Selected interatomic distances [Å] and angles of the anion in 2 [°]: BiÀ Bi 2.9086(9)-3.0840 (16), ZnÀ Bi 2.786(7)-2.840(2); Bi2À Zn1À Bi3 98.06( 6), Bi3À Zn1À Bi8 123.67 (7), Bi3À ZnÀ Bi10 108.89( 6), Bi1À Zn1À Bi8 115.16, Bi1À Zn1À Bi10 113.66( 6), Bi8À Zn1À Bi10 98.02 (5).…”

“…[15] Additionally, the existence of (protonated) binary nortricyclane-type anions was reported, (SiPn 6 H 2 ) 2À (Pn = P, As). [16] In which one of the Pn atoms was replaced with Tt À , together indicating that even these two cages are labile in some regard.…”

“…In spite of the dominance of retained Pn 7 3− cages in reaction products using these units, there are also some reports of their fragmentation upon corresponding treatment, such as [Co(η 5 ‐P 5 ){η 2 ‐P 2 H(Mes)}] 2− , [13] [As@Ni 12 @As 20 ] 3− , [14] or [Co(η 3 ‐As 3 ){η 4 ‐As 4 (Mes) 2 }] 2− [15] . Additionally, the existence of (protonated) binary nortricyclane‐type anions was reported, (SiPn 6 H 2 ) 2− (Pn=P, As) [16] . In which one of the Pn atoms was replaced with Tt − , together indicating that even these two cages are labile in some regard.…”

K2Ge3As3: Fiberlike Crystals of a Narrow-Band-Gap Zintl Phase with a One-Dimensional Substructure ∞1{(Ge3As3)2–}

“…Irrespective of the dimensionality of the underlying solid-state compound, many of these compounds have furthermore been used in the recent past for the preparation of soluble salts of molecular binary Zintl anions. − The latter are of great interest as precursors for the targeted synthesis of ternary intermetalloid clusters, ,− which we have intensively studied over the past years regarding their synthesis and formation mechanisms and, finally, the chemical and physical properties of multimetallic particles. As many of the ternary phase diagrams of A/E′/E″ (A = alkali metal, E′, E″ = elements from groups 13, 14, and 15, respectively) are still unknown, most of the mentioned salts were formed in an explorative manner by permutation of the compositions of the ternary mixtures to improve purities and yields.…”