Small Variations, Big Impact: Structural Diversity of the Complexes of a Phosphane‐Decorated Benzenedithiol with Group‐11 Metals

Simon H Schlindwein,Martin Nieger,Dietrich Gudat

doi:10.1002/ejic.202001026

Simon H Schlindwein, Martin Nieger + Show 1 more

Open Access

https://doi.org/10.1002/ejic.202001026

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Abstract

AbstractReaction of a phosphane‐decorated benzenedithiol (pbdtH2) with coinage metal salts furnished polynuclear complexes [M2(pbdtH)2] (M=AuI) or [cat][M5(pbdt)3] (cat=unipositive cation, M=AgI, CuI), which were characterized by analytical and spectroscopic techniques and single‐crystal X‐ray diffraction studies. Furthermore, a double salt with an anion [Ag5(pbdt)3(PPh3)]− that proved unstable in solution was characterized crystallographically. The spectroscopic and crystallographic data revealed that the Cu(I) and Ag(I) complexes exhibit, despite their like stoichiometric composition, isomeric molecular structures. The observed disparities were reproduced by DFT studies. The dinuclear Au(I) complex was found to undergo air‐oxidation to furnish a mixed‐valent complex [(AuIII)2(AuI)2(pbdt)4]. The copper(I) – but not the isomeric silver(I) complexes – showed luminescence in the solid state.

Highlights

P,S-based hybrid ligands[1] have received less attention than hetero-bidentate ligands featuring combinations of phosphorus with other heteroatoms like oxygen and nitrogen, they have attracted some interest in catalysis[2] and can act as bridging ligands[3] which support the assembly of multinuclear complexes
We report on the reactions of 1 with salts of univalent coinage metal cations
To study its coordination behavior towards gold(I), we treated ligand 1 with [Au(tht)Cl]. This compound allows for reactions under substitution of both the tht- and chlorido-ligands and was deemed an ideal source of Au(I) cations for the assembly of polynuclear complexes with anionic phosphane-benzenedithiolates

Summary

Introduction

P,S-based hybrid ligands[1] have received less attention than hetero-bidentate ligands featuring combinations of phosphorus with other heteroatoms like oxygen and nitrogen, they have attracted some interest in catalysis[2] and can act as bridging ligands[3] which support the assembly of multinuclear complexes. While the different donor atoms retain a certain electronic disparity, their common preference to bind to ’soft’ metal centers enabled the use of 1 as scaffold to assemble di- and trinuclear homometallic complexes with group-10 metal centers and a first example of a heterometallic complex 2 comprising both group-10 (Pd) and group-11 metal ions (Au).[5] Based on these results, we reasoned that 1 might support the formation of polynuclear complexes containing exclusively coinage metals Target compounds of this type have previously attracted some interest because of their luminescence properties.[6] Here, we report on the reactions of 1 with salts of univalent coinage metal cations,

University of Helsinki

Results and Discussion

Conclusion

Experimental Section