Orthogonal ligand scaffolds, consisting of soft and hard donor sites, are useful tools for the selective synthesis of heteronuclear coinage metal compounds, controlling their coordination geometry and tuning their photophysical properties.
The synthesis of a novel bis-stannylene pincer ligand and its complexation with coinage metals (Cu I , Ag I and Au I ) are described. All coinage metal centres are in tetrahedral coordination environments in the solid state and are exclusively coordinated by four neutral Sn II donors. 119 Sn NMR provided information about the behaviour in solution. All of the isolated compounds have photoluminescent properties, and these were investigated at low and elevated temperatures. Compared to the free bis-stannylene ligand, coordination to coinage metals led to an increase in the luminescence intensity. The new compounds were investigated in detail through all-electron relativistic density functional theory (DFT) calculations.
A bis(diphenyl)-phosphine functionalized ß-diketimine ligand (PNac-H) was applied for the synthesis of a subvalent Ni(I) complex [PNac-Ni]. Here, the Ni(I) center is stabilized by a tetradentate PNNP-type pocket, forming a square planar coordination sphere. Subsequently, the Ni(I) complex was investigated with regard to its reactivity and the activation of small molecules. The reductive potential of Ni(I) enabled an activation of different substrate classes, such as CH 2 X 2 (X=Br, I), I 2 or Ph 2 E 2 (E=S, Se). The ligand's design allows a stabilization of the reactive Ni(I) species while at the same time enabling activation processes due to a hemilabile coordination behavior and accessible axial coordination sites. The activation products have been characterized by single crystal X-ray diffraction, NMR and IR spectroscopy as well as elemental analysis.
Binuclear gold(i) amidinate compounds with a variety of sidechains were synthesised. The photoluminescence properties of these compounds were investigated and analysed by quantum chemical calculations.
The sterically demanding 1,8-bis(3,5-ditertbutylphenyl)-3,6-di-tert-butylcarbazole (dtbpCbz)–H was deprotonated with various metal bases to obtain a complete series of thermally robust alkali metal compounds of the type [(dtbpCbz)M] (M = Li, Na,...
The reaction of a bis(stannylene)-pincer-type ligand with coinage metal precursors led to tetrahedral coordination modes in the solid state not only for copper, but also for silver and gold. This is rather unusual for the heavier coinage metal ions, as linear coordination is favored. NMR studies revealed the behavior in solution, showing a significant distortion from the tetrahedral coordination for the gold compound. These findings were underlined by allelectron relativistic density functional theory (DFT) calculations.
A novel bis‐stannylene pincer‐type ligand has been prepared for the exclusive tetrahedral coordination of coinage metals. All compounds feature photoluminescent properties in the solid state. Detailed investigations by all‐electron relativistic density functional theory calculations were performed. More information can be found in the Research Article by P. W. Roesky and co‐workers (DOI: 10.1002/chem.202203583). Cover artwork by Alicia Schmidt.
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