A versatile salt-metathesis route to heteroatomic clusters derived from phosphorus and arsenic Zintl anions

Abstract

Salt metathesis reactions between ethylenediamine (en) solutions of the K(3)E(7) (E = P, As) Zintl phases and post-transition metal halides (InCl(3), TlCl, SnI(2) and PbI(2)) have yielded a family of novel heteroatomic cluster anions, [In(E(7))(2)](3-), [TlE(7)](2-) and [E'E(15)](3-) (E' = Sn, Pb; E = P, As). Several of these new species have been characterized by single-crystal X-ray diffraction as salts of sequestered potassium cations in [K(2,2,2-crypt)](3)[In(P(7))(2)]·3.5py (1), [K(2,2,2-crypt)](2)[TlP(7)]·py (3), [K(18-crown-6)](2)[TlAs(7)] (4b), [K(2,2,2-crypt)](3)[E'P(15)]·en (E' = Sn (5), Pb (6)) and [K(2,2,2-crypt)](3)[SnAs(15)]·2en (7). The presence of all of the cluster anions in solution was confirmed by electrospray mass-spectrometry and by (1)H and (31)P{(1)H} NMR spectroscopy when pertinent.

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

“…This electron fluctuation is observable over the whole basin system. [1,2,4] and bond lengths and angles in all components are in good agreement with similar As 7 3-or Sb 7…”

“…The molecular motif with the general formula E 15 M 3-, which can be derived from two nortricyclane cages linked by an E-M unit was reported by Goicoechea in 2011. [1] In this case, starting compounds were K 3 E 7 (E = P, As), TI 2 15 Hg was synthetized by Sen [2] in 2012 by the reaction between K 3 As 7 and Hg(C 6 [5] In this paper we present the new compounds [Rb( [18] …”

New Compounds with [As7]3– Clusters: Synthesis and Crystal Structures of the Zintl Phases Cs2NaAs7, Cs4ZnAs14 and Cs4CdAs14

“…The same bonding features have also been revealed for the cluster compounds which have the similar structural motif, e.g., [K(2,2,2-crypt)] 3 [In(P 7 ) 2 ]3.5py [21], [K(2,2,2-crypt)] 4 ZnE 14 (E = P, As) [22], and [K(2,2,2-crypt)] 4 CdP 14 6py [22]. The Zn-As bond distances fall in the range 2.514 to 2.598 Å, comparing well with the sum of their covalent radii [23], as well as with the corresponding distances found in other Zintl compounds with Zn-As bonding such as Ba 2 ZnAs 2 [24], Eu 11 Zn 6 As 12 [25], and RbZn 4 As 3 [26].…”

Zintl Salts Ba2P7X (X = Cl, Br, and I): Synthesis, Crystal, and Electronic Structures

“…Heavier analogs of such clusters with As and Sb are also known [16][17][18]. Similar to other intermetallics, the electronic structures of polyphosphides can be rationalized by application of the Zintl concept [19,20].…”