Crystal structures of chloro(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)Cl2, and dihydroxo(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)(OH)2, and two-stage hydrolysis of its homologue dimethoxo(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)(OMe)2
作者:Shwu-Juian Lin、Yao-Jung Chen、Jyh-Horung Chen、Feng-Ling Liao、Sue-Lein Wang、Shin-Shin Wang
DOI:10.1016/s0277-5387(97)00011-9
日期:1997.1
The crystal structures of chloro(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)Cl-2, dimethoxo(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)(OMe)(2), and dihydroxo(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)(OH)(2), were determined. The coordination sphere of the Ge4+ ion is a distorted octahedron in which the apical sites are occupied by two monodentate Cl- (or OMe- OH-) groups. The geometry around the germanium centre of the Ge(tpp)Cl-2 molecule has Ge(1)-Cl(1) = 2.262(1) and Ge(1)-N(1) = 2.019(2) Angstrom. In the structure of Ge(tpp)(OMe)(2) the germanium(1)-oxygen distance is 1.826(3), average Ge(I)-N = 2.032(3), and O(1)-C(23) = 1.331(6) Angstrom. The structure of Ge(tpp)(OH)(2) has Ge(1)-O(1) = 1.809(3) and Ge(I)-N(I) - 2.027(2) Angstrom., Two-stage hydrolysis of Ge(tpp)(OMe)(2) was studied by H-1 and C-13 NMR spectroscopy. The use of a limited amount of water in CDCl3 (or CD2Cl2) allowed the hydrolysis intermediate, hydroxomethoxo(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)(OMe) (OH), and hydrolysis product, dihydroxo(meso-tetraphenylporphyrinato) Ge(tpp)(OH)(2), to be identified, X-ray diffraction data and solid-state C-13 CP/MAS spectra of Ge(tpp)(OMe)(2) provide evidence for two monodentate methoxo groups coordinated to the germanium(IV) atom. (C) 1997 Elsevier Science Ltd.