- Article
Reactions of Benzylsilicon Pyridine-2-olate BnSi(pyO)3 and Selected Electrophiles—PhCHO, CuCl, and AgOTos
- Saskia Münzner,
- Erica Brendler and
- Jörg Wagler
In dynamic equilibria, benzylsilicon pyridine-2-olate (BnSi(pyO)3, L) and benzaldehyde react with addition of the Si(pyO) moieties to the PhHC=O carbonyl group and formation of compounds BnSi(–O–C(H,Ph)–N(2-pyridone))x(pyO)3−x (L’, L’’, and L’’’, for x = 1, 2, 3, respectively). Addition of CuCl to a solution containing L, L’, L’’, and L’’’ results in the formation of BnSi(pyO)3CuCl (LCuCl), shifting the equilibrium towards L with liberation of benzaldehyde. In THF as a solvent, the reaction of L in the presence of excess CuCl affords the complex LCuClCuCl. Upon dissolving in chloroform, it transforms into LCuCl with precipitation of CuCl. The solid state structure of LCuClCuCl features both the monomeric complex with CuClCuCl pattern and a dimer thereof with CuClCu(Cl)2CuClCu pattern and a central Cu2Cl2 four-membered ring. This dimer of LCuClCuCl is the first crystallographically characterized representative of this Cu(I)-only Cu4Cl4 motif. The reaction of LCuCl and silver tosylate (AgOTos) in THF affords LCuOTos with precipitation of AgCl, whereas LAgOTos was obtained from L and AgOTos. In the crystal structure, LAgOTos features tetracoordinate Ag(I) in a distorted tetrahedral AgN3O coordination sphere and a short Ag···Si trans-annular contact (3.3245(7) Å). 109Ag NMR spectroscopy indicates a change in the coordination in solution, with δ 109Ag = +551 and +419 ppm in the solid and in CDCl3 solution, respectively. In combination, 29Si NMR spectroscopy indicates changes in the Si coordination sphere, with δ 29Si = −74.2 and −66.5 ppm in the solid and in CDCl3 solution, respectively. Conversion of LAgOTos with tetraethylammonium chloride results in the precipitation of AgCl with release of L.
1 January 2026



