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

Niklas Rinn,Stefanie Dehnen,Han Yu Hou,Lukas Guggolz

doi:10.1002/chem.202101139

Abstract

Fragmentation reactions of organotetrel chalcogenide heteroadamantane‐type clusters [(PhT)4E6] (T/E=Si/S (1); Si/Se; Sn/S, and Sn/Se) by addition of the corresponding sodium chalcogenide gave salts of the general formula Na3[PhTE3], with T/E=Si/S (2); Si/Se (3); Sn/S (A); Sn/Se (4). Reaction of these salts with [Cu(PPh3)3Cl] gave a series of organotetrel–copper chalcogenide clusters [(CuPPh3)6(PhTE3)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 {PhTE3} units coordinating a Cu6 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 [(CuPPh3)6(PhSnSe3)3Cu3SnSe] (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.

Highlights

By addition of [Cu(PPh3)3Cl] to 2, 3, or A in dichloromethane (DCM), we obtained the expected series of cluster compounds [(CuPPh3)6(PhSiS3)2] (5), [(CuPPh3)6(PhSiSe3)2] (6), and [(CuPPh3)6(PhSnS3)2] (7) after filtration of the reactive solutions and layering with n-hexane. 5–7 share their common cluster core architecture with that of known compounds [(CuPPhMe2)6(PhSnS3)2][40] and [(CuPPh3)6(RCOGeS3)2] (RCO=Me(O) CCH2CMe2),[38] both which were obtained in one-pot reactions starting out from the respective heteroadamantane-type cages, without isolation and clarification of the starting material
From the corresponding reaction of 4 with the Cu(I) source, two different cluster compounds can be isolated depending on the crystallization conditions
Compound [(CuPPh3)6(PhSnSe3)2] (8) crystallizes from a more concentrated filtrate within 24 hours, while layering of a more diluted solution with nhexane selectively leads to the formation of single crystals of [(CuPPh3)6(PhSnSe3)3Cu3SnSe] (9) within one week. 9 exhibits an extended cluster core with idealized C3v symmetry and signs of a partial degradation of the [PhSnSe3]3À moiety

Summary

Introduction

Compound 1, comprising the heteroadamantane-type cluster [(PhSi)4Se6], crystallizes in the monoclinic space group P21/c and exhibits the expected molecular structure (Figure 1). The cluster in compound 7 (T/E = Sn/S; Figure 3c) differs by its phosphine ligands only from the reported, prototypic cluster [(CuPPhMe2)6(PhSnS3)2].[40] It possesses a lower molecular symmetry than the two lighter congeners, which is reflected in a broader range of Cu···Cu distances (2.713(2)–3.278(3) Å) as can be taken from significantly larger thermal displacement parameters of the atoms than observed for the analogous compounds, compound 7 has only little tendency to crystallize.

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Conclusion