The Hexacoordinate Si Complex SiCl4(4-Azidopyridine)2—Crystallographic Characterization of Two Conformers and Probing the Influence of SiCl4-Complexation on a Click Reaction with Phenylacetylene

4-Azidopyridine (1) and SiCl4 react with the formation of the hexacoordinate silicon complex SiCl4(4-azidopyridine)2 (2). Upon dissolving in warm chloroform, the complex dissociates into the constituents 1 and SiCl4 and forms back upon cooling. Depending on the cooling, two different crystalline modifications of 2 were obtained, which feature two different trans-conformers. Slow cooling to room temperature afforded conformer 2′, which features coplanar pyridine rings. Rapid cooling to −39 °C afforded crystals of conformer 2″, in which the planes of the pyridine ligands are nearly orthogonal to one another. Whereas 2′ resembles the molecular arrangement of various other known SiX4(pyridine)2 (X = halide) complexes, 2″ represents the first crystallographically confirmed example of a SiX4(pyridine)2 complex in this conformation. Conformers 2′ and 2″ were studied with 13C and 29Si solid state NMR spectroscopy. Their differences in 29Si chemical shift anisotropy, as well as energetic differences, were further investigated with computational analyses. In spite of the similar stabilities of the two conformers as isolated molecules, the crystal packing of 2″ is less stable, and its crystallization is interpreted as a kinetically controlled effect of seed formation. (3+2)-cycloaddition of 1 and phenylacetylene in toluene at 110 °C yields a mixture of 1-(4-pyridyl)-4-phenyl-1,2,3-triazole (1,4-3) and 1-(4-pyridyl)-5-phenyl-1,2,3-triazole (1,5-3) in approximate 1:2 molar ratio. The crystal structures of the two isomers were determined via X-ray diffraction. In chloroform (at 60 °C), this reaction is slow (less than 2% conversion within 4 h), but the presence of SiCl4 enhanced the rate of the reaction slightly, and it shifted the triazole isomer ratio to ca. 1:6 in favor of 1,5-3.