Abstract
A series of pyridine-2-olates (pyO) and pyridine-2-thiolates (pyS) of silicon was studied in solid state and in solution. The crystal structures of Me3Si(pyO) (1a), Me3Si(pyS) (1b), Me2Si(pyO)2 (2a), Me2Si(pyS)2 (2b), Ph2Si(pyO)2 (3a) and Ph2Si(pyS)2 (3b) were determined by X-ray diffraction. For that purpose, crystals of the (at room temperature) liquid compounds 1a and 1b were grown in a capillary on the diffractometer. Compounds 1a, 1b, 2a, 2b and 3a feature tetracoordinate silicon atoms in the solid state, whereas 3b gave rise to a series of four crystal structures in which the Si atoms of this compound are hexacoordinate. Two isomers (3b1 with all-cis arrangement of the C2N2S2 donor atoms in P1¯, and 3b2 with trans S-Si-S axis in P21/n) formed individual crystal batches, which allowed for their individual 29Si NMR spectroscopic study in the solid state (the determination of their chemical shift anisotropy tensors). Furthermore, the structures of a less stable modification of 3b2 (in C2/c) as well as a toluene solvate 3b2 (toluene) (in P1¯) were determined. In CDCl3, the equimolar solutions of the corresponding pairs of pyO and pyS compounds (2a/2b and 3a/3b) showed substituent scrambling with the formation of the products Me2Si(pyO)(pyS) (2c) and Ph2Si(pyO)(pyS) (3c), respectively, as minor components in the respective substituent exchange equilibrium.
Subject
Inorganic Chemistry,Condensed Matter Physics,General Materials Science,General Chemical Engineering
Cited by
4 articles.
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