Solution Dynamics and Gas-Phase Chemistry of Pd₂@Sn₁₈⁴⁻

Abstract

Sn9(4-) reacts with Pd(PPh3)4 in ethylenediamine/toluene solvent mixtures in the presence of 2,2,2-cryptand to give the Pd2@Sn18(4-) cluster as the K(2,2,2,-crypt)+ salt. The cluster is isostructural with Pd2@Ge18(4-) and has a nuclearity different from that of the Pt and Ni analogues, Ni2@Sn17(4-) and Pt2@Sn17(4-). The Pd2@Sn18(4-) ion has a deltahedral capsulelike structure with 40 cluster bonding electrons and is the largest free-standing polystannide characterized to date. Like Pt2@Sn17(4-), the Pd2@Sn18(4-) complex is highly dynamic in solution, showing a single (119)Sn NMR resonance indicative of an intramolecular liquidlike dynamic exchange. LDI-MS studies of the crystalline sample show extensive fragmentation and the formation of five gas-phase cluster series: Sn(x)- (1 < x < 12), PdSn(x-1) - (4 < x < 18), Pd 2Sn(x-2) - (6 < x < 21), Pd3Sn(x-3) - (8 < x < 21), and Pd 4Sn(x-4) - (13 < x < 21). The most abundant ion in the gas phase is the PdSn(10) - cluster, which presumably has an Sn(10) bicapped-square-antiprismatic structure with an endohedral Pd (e.g., Ni@Pb(10)(2-)).

Developing organo-Zintl deltahedral clusters as ligands for coordination to transition-metals via their organic tethers

“…(2) The Zintl clusters can be capped by a metal or an organometallic-metal fragment as in [E 9 [13], [(PdePd)@Ge 18 ] 4- [14], [(PdePd)@Sn 18 ] 4- [15], [Ni 3 @(Ge 9 ) 2 ] 4- [16], and [M 2 @Sn 17 ] 4-(where M ¼ Ni, Pt) [2h,17].…”

The closo‐[Sn9Ir(cod)]3– and [Pb9Ir(cod)]3– Zintl Ions: Isostructural IrI Derivatives of the nido‐E94– Anions (E = Sn, Pb)

“…Examples include [ 18 2-(E = Ge, Sn). [3,[5][6][7][8][9] While 9-vertex and 10-vertex clusters are known with and without endohedral atoms, structures with more than 10 vertices are expected to have interstitial atoms when prepared in solution or the solid state. [1] All of these complexes can be described as derivatives of Wade-Mingos type deltahedral clusters with the exception of the recent theoretical and experimental results showing the remarkable non-deltahedral structures in the D 5h -[M@Ge 10 ]…”

Reactions of exo‐Substituted RSn93− Clusters with Pd: Endohedral Cluster Formation and Oxidative Insertion

“…[13,14] The endohedral Pd1 atom causes the 119 Sn resonances of both 2 and 3 to shift downfield relative to the noncentered [Sn 9 SnCy 3 ] 3À cluster 1 (Table 3). In addition, the intracluster Sn,Sn coupling constants were significantly reduced relative to 1 due to expansion of the Sn 9 framework.…”