Coupling Reactions of Functionalized Zintl Ions [E₉Cd(C₆H₅)]³⁻ (E = Sn, Pb) with Tributyltinhydride: Synthesis and Isolation of {Sn₉CdSn[(CH₂)₃CH₃]₃}³⁻

Abstract

Reaction of ethylenediamine solutions of K(4)E(9) (E = Sn, Pb) with diphenylcadmium yielded the Cd(C(6)H(5))-functionalized Zintl ions, closo-[E(9)Cd(C(6)H(5))](3-) (E = Sn (1); Pb (2)). Solution reactivity studies of 1 with tributyltinhydride in pyridine revealed that the cluster is capable of undergoing a coupling reaction to yield the tributyltin-functionalized cluster, closo-{Sn(9)CdSn[(CH(2))(3)CH(3)](3)}(3-) (3). In-situ monitoring of this reaction by (1)H and (13)C{(1)H} NMR spectroscopy reveals the formation of the tributyltin functionalized cluster anion in addition to free benzene. Species 1-3 were characterized in the solid-state as [K(2,2,2-crypt)](+) salts by single crystal X-ray diffraction and elemental analysis, while the presence of all three cluster anions in solution was confirmed by (1)H and (13)C{(1)H} NMR spectroscopy and electrospray mass-spectrometry.

Step‐by‐Step Synthesis of the Endohedral Stannaspherene [Ir@Sn12]3− via the Capped Cluster Anion [Sn9Ir(cod)]3−

“…The Sn-Sn distances along the edges of the polyhedron range from 2.9256(9) to 3.2035 (9) and thus are close to those reported previously for Sn 9 clusters capped by transition-metal organometallic fragments such as M''(CO) 3 (M'' = Cr, Mo, W), [28] ZnPh, [29] and CdPh. [30] The Ir-Sn distances are in the range of 2.7605(7) to 2.7772 (6) . Chemical bonding in 1 a can be discussed in analogy to the Scheme 1.…”

Varying Bonding Modes of the Zintl Ion [Ge9]4– in CuI Complexes: Syntheses and Structures of [Cu(η4‐Ge9)(PR3)]3– (R = iPr, Cy) and [Cu(η4‐Ge9)(η1‐Ge9)]7–

“…[22] Further, [Ni(η 4 -Ge 9 )(CO)] 3-was presented as the only known paramagnetic E 9 cluster complex and the only example with a group 10 element in capping position to an empty nido E 9 cluster. [23] The synthesis of [Ir(η 4 -Sn 9 )(cod)] 3-(cod = cyclooctadiene) currently proved that group 9 elements can also be coordinated to an E 9 cluster.…”

Synthesis and Crystal Structure of a Salt Containing ∞1{Zn[trans‐μ2(η3:η3‐Ge9)]}2– Anions: A Polymer with Ge9 Zintl Clusters Bridged by Zn Atoms

“…[38] h: height of the prism, e: length of the base of the trigonal prism, c: distance to the capping Ge atoms, γ: deviation from coplanarity of opposite triangular faces of the trigonal prism. [39] Cluster [23,25,44] In contrast, the reaction of elemental mercury leads to the polymeric anion ϱ 1 [Hg(Ge 9 )] 2-with Hg linking the Ge 9 clusters, [37,45,46] Figures S3 and S4), whereas crystalline Zn powder could not be detected. In addition to the signals of Zn 2 (Mesnacnac) 2 , resonances originating from small amounts of MesnacnacH were observed in the 1 H NMR spectrum ( Figure S4b) of the extract of the residue, clearly indicating that the Zn I complex was at least partially protonated.…”