Systematic Access of Ternary Organotetrel‐Copper Chalcogenide Clusters by [PhTE₃]³⁻ Anions (T=Si, Sn; E=S, Se)

Abstract

Reaction of these salts with [Cu(PPh 3 ) 3 Cl] gave a series of organotetrel-copper chalcogenide clusters [(CuPPh 3 ) 6 (PhTE 3 ) 2 ] with T/E = Si/S; (5), Si/Se (6), Sn/S (7) and Sn/Se (8).Compounds 5-8 share a common structural motif with two intact {PhTE 3 } units coordinating a Cu 6 moiety, which was previously reported with other ligands, and for the Sn and Ge congeners only. If the Sn/Se reaction system was allowed to crystallize more slowly, single crystals of compound [(CuPPh 3 ) 6 (PhSnSe 3 ) 3 Cu 3 SnSe] (9) were obtained, which are based on a larger cluster structure. Hence, 9 might form from 8 through incorporation of additional cluster fragments. The experimentally and quantum chemically determined optical properties were compared to related clusters.

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

“…While at first reactions were carried out using gaseous H2E (E = S, Se) and a group 14 halide RQX3, [303][304][305] most hybrid materials can be obtained through route D, using a solid or liquid chalcogenide source A2E (A = alkaline metal, SiMe3; E = S, Se) to prepare 565-612 (Figure 13). [306][307][308][309][310][311][312][313][314][315][316][317][318][319][320][321][322] As some of them are sensitive to water, the (SiMe3)2E precursors are often advantageous for their solubility in organic solvents. The clusters' structure is heavily influenced by their organic component.…”

“…EtSiCl3, H2Se, Al / 150 °C, 3 h F [304] [(ThexSi)4Se6] (573) 1. Li2S, ThexSiCl3 / THF, 0 °C to RT, 5 days 2. decaline, 150 °C, 3 h D [306,307] [(PhSi)4Se6] (574) Na2Se, PhSiCl3 / THF, 0 °C, 18 h D [308] [(MeGe)4S6] (575)…”

“…13). [306][307][308][309][310][311][312][313][314][315][316][317][318][319][320][321][322] As some of them are sensitive to water, the (SiMe 3 ) 2 E precursors are oen advantageous for their solubility in organic solvents. The clusters' structure is heavily inuenced by their organic component.…”