Hypervalency of Organogermanium Compounds-Scope and Limitation

有机锗化合物的高化合价 - 范围和限制

• 批准号: 11640547
• 负责人: TAKEUCHI Yoshito
• 金额: $ 2.18万
• 依托单位: Kanagawa University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11640547/
• 关键词: Organogermanium compounds; dynamic NMR method; hyper coordination; pseudorotation; prototropy; Xray crystallographic analysis; trigonal bipyramid; high resolution solid state NMR; 固体高分解能Ge-73NMR; 有機ゲルマニウム化学; Ge-73 NMR

1 The structure of hypercoordinate organogermanium comounds in solid-ohase and in solution.The structure of 2-(2-t-butyl-5-oxo-1, 3, 2-oxathiagermolan-2-ylthio) acetic acid (1) and its phenyl derivative (2) and their pyridiumu salts (3) and (4) was investigated. In the solid phase, all compounds investigated were in trigonal bipyramidal structure.In solid-state, the two trigonal bipyramids are different while in solution these are equivalent in the NMR timescale. Thus, there is observed only one CH_2 proton and carbon signals, indicating a rapid exchange. Furthermore, the methylene peak split into two peaks, indicating a slow exchange. The barrier is ca 12 kcal mol^<-1>. We believe this exchange is Berry pseudorotation or turnstile rotation.2 Hypercoordinate structure of triarylgermanes.We prepared a variety of triarylgermanes with some ligands at ortho position such as chlorotris [2-(methoxymethyl) phenyl] germane and methyltris [2-(methoxymethyl)-phenyl] germane. Both compounds are pentavalent in a trigonal bipyramidal structure. The reason why such compounds did not show hexa or hepta coordination is not clear at all.3 Synthesis of novel hosts modified with germanium.We prepared a variety of novel organogermanium compounds as possible hosts for anions and neutral molecules. These include calixarenes with some side-chain containing germanium, azacrown with germanium-containing side-chain on nitrogen, and cyclophanes including germanium in the bridge.4 High-resolution solid-state ^<73>Ge NMR spectroscopy.We firstly observed germanium resonance of solid tetraphenylgermane in high-resolution condition. Ge-73 NMR may be a powerful tool for studying hyper valency of germanium.

1超配位有机锗化合物在固相和溶液中的结构研究了2-（2-叔丁基-5-氧代-1，3，2-氧硫杂茂烷-2-基硫代）乙酸（1）及其苯基衍生物（2）和它们的吡啶盐（3）和（4）的结构。在固相中，所研究的化合物均为三角双锥结构，在固体中，两个三角双锥在NMR时间尺度上是不同的，而在溶液中，它们在NMR时间尺度上是等价的。因此，只有一个CH_2质子和碳信号，表明快速交换。此外，亚甲基峰分裂成两个峰，表明交换缓慢。势垒约为12千卡/摩尔<-1>。2.三芳基锗烷的超配位结构我们合成了一系列三芳基锗烷，如氯代三[2-（甲氧基甲基）苯基]锗烷和甲基三[2-（甲氧基甲基）苯基]锗烷。这两种化合物都是五价的三角双锥结构。这类化合物没有显示六配位或七配位的原因还不清楚。3.新型锗修饰主体的合成我们制备了多种新型有机锗化合物作为阴离子和中性分子的可能主体。这些化合物包括某些侧链含锗的杯芳烃、氮原子上含锗侧链的氮杂冠醚和桥上含锗的环番。4高分辨固体~ <73>1Ge NMR谱我们首次在高分辨条件下观察到固体四苯基锗烷的锗共振。Ge-73 NMR可能是研究锗的高价态的有力工具。

项目成果

Y.Takeuchi,T.Sakurai: "The synthesis and possible transport property of a calix [4] arene modified with sidechains containing germanium"Main Group Metal Chem.. 23(5). 311-317 (2000)

Y.Takeuchi，T.Sakurai：“用含锗侧链修饰的杯[4]芳烃的合成和可能的传输特性”Main Group Metal Chem.. 23(5)。

Y.Takeuchi, M.Nishikawa, K.Tanaka, T.Takayama, M.Imanari, K.Deguchi, T.Fujito and Y.Sugisaka: "The first observation of high-resolution solid-state ^<73>Ge NMR spectra of organogermanium compounds."Chem.Commun.. 687 (2000)

Y.Takeuchi、M.Nishikawa、K.Tanaka、T.Takayama、M.Imanari、K.Deguchi、T.Fujito 和 Y.Sugisaka：“高分辨率固态 ^<73>Ge NMR 谱的首次观察

Y.Takeuchi et al.: "The Synthesis and Possible Transport Property of a calix[4]arene modified with sidechains Containing germanium"Main group Matal Chemistry. (in press). (2000)

Y.Takeuchi 等人：“用含锗侧链修饰的杯[4]芳烃的合成和可能的传输特性”主组金属化学。

Y.Takeuchi,M.Nishikawa,etc: "First observation of high-resolution solid state Ge-73 NMR Spectra of organogermanium compounds."Chem.Commun.. 687-688 (2000)

Y.Takeuchi，M.Nishikawa，等：“首次观察有机锗化合物的高分辨率固态Ge-73 NMR光谱。”Chem.Commun.. 687-688 (2000)

Y.Takeuchi et al: "The First Observation of high-resolution solid-state 73Ge NMR Spectra"J. Chem. Soc. Chem. Communications. (in press). (2000)

Y.Takeuchi 等人：“高分辨率固态 73Ge NMR 谱的首次观察”J。