Structure of (tropolonato)4M-Type Compounds (M = Si, Ge, Sn)
摘要:
T4M (M = Si, Ge, Sn; T = tropolonato)-type compounds were synthesized by reactions of tropolone with tetramethoxysilane, tetramethoxygermane, and tetrachlorostannane, respectively. X-ray and NMR analyses have shown that, both in the solid state and in solution, T4Si exists as an ion pair of a hexacoordinate silicocation (T3Si+) with an associated tropolone anion (T-), while T4Sn has an octacoordinate structure. The geometry around the tin atom is best described as a bicapped trigonal prism distorted toward a dodecahedron, in which the eight oxygen atoms of four tropolonato ligands are coordinated to a tin atom with an average Sn-O bond distance-of 2.168 Angstrom. Features of NMR and UV-vis spectra of T4Ge are similar to those of T4Si, indicating ion pairing between T3Ge+ and T- in solution; the black color of the solid of T4Ge is suggestive of the ion pairing in the solid-state as well, whereas single crystals suitable for X-ray analysis have not been obtained.