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

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Schlindwein , S H , Nieger , M & Gudat , D 2021 , ' Small Variations, Big Impact : Structural Diversity of the Complexes of a Phosphane-Decorated Benzenedithiol with Group-11 Metals ' , European Journal of Inorganic Chemistry , vol. 2021 , no. 8 , pp. 748-755 . https://doi.org/10.1002/ejic.202001026

Title: Small Variations, Big Impact : Structural Diversity of the Complexes of a Phosphane-Decorated Benzenedithiol with Group-11 Metals
Author: Schlindwein, Simon H.; Nieger, Martin; Gudat, Dietrich
Contributor: University of Helsinki, Department of Chemistry
Date: 2021-02-25
Language: eng
Number of pages: 8
Belongs to series: European Journal of Inorganic Chemistry
ISSN: 1434-1948
URI: http://hdl.handle.net/10138/328061
Abstract: Reaction of a phosphane-decorated benzenedithiol (pbdtH(2)) with coinage metal salts furnished polynuclear complexes [M-2(pbdtH)(2)] (M=Au-I) or [cat][M-5(pbdt)(3)] (cat=unipositive cation, M=Ag-I, Cu-I), which were characterized by analytical and spectroscopic techniques and single-crystal X-ray diffraction studies. Furthermore, a double salt with an anion [Ag-5(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 [(Au-III)(2)(Au-I)(2)(pbdt)(4)]. The copper(I) - but not the isomeric silver(I) complexes - showed luminescence in the solid state.
Subject: Sulfur ligands
Phosphane ligands
Coinage metals
Bridging ligands
Aggregation
COORDINATION CHEMISTRY
PHOSPHORUS
LIGANDS
ENANTIOSELECTIVITY
DESIGN
AU
116 Chemical sciences
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