二氢化锗与一氧化二氮、三甲基叠氮硅烷、酮和炔烃的反应以及甲基类似物与三甲基硅基重氮甲烷的反应。

Reactivity of germanium(II) hydride with nitrous oxide, trimethylsilyl azide, ketones, and alkynes and the reaction of a methyl analogue with trimethylsilyl diazomethane.

机构信息

Institut für Anorganische Chemie, Universität Göttingen, Tammannstrasse 4, 37077, Göttingen, Germany.

出版信息

Dalton Trans. 2010 Jan 7(1):132-8. doi: 10.1039/b914164b. Epub 2009 Oct 5.

PMID:20023943

Abstract

The reactions of stable beta-diketiminate germanium(II) hydride LGeH (1) [L = HC(CMeNAr)2, Ar = 2,6-iPr2C6H3] with nitrous oxide, trimethylsilyl azide, ketones, and alkynes are described. 1 reacts with nitrous oxide to yield the germanium(II) hydroxide LGeOH (2), and with trimethylsilyl azide affords in toluene at room temperature the germanium(II) azide LGeN3 (3), and also the germanium(IV) diamide L'Ge(NHSiMe3)2 (L' = CH{(CCH2)(CMe)(2,6-iPr2C6H3N)2}) (4). Ketones (PhCOCF3, 2-C4H3SCOCF3) and 1 generated the germanium(II) alkoxides (5-6) in high yield. The activated terminal alkyne (HC[triple bond]CCO2Me) and disubstituted alkyne (EtO2CC[triple bond]CCO2Et) react with 1 to form the germanium(II) substituted alkenes (vinyl germylene) (7-8). Further reaction of the methylgermanium(II) compound LGeMe (9) with trimethylsilyl diazomethane resulted in the formation of germanium(IV) amide L'Ge(Me)NHN=CHSiMe3 (10). Compounds 2-8, and 10 were characterized by microanalysis and multi-nuclear NMR spectroscopy. Furthermore compounds 3-6, and 8 are confirmed by X-ray structural analysis.

摘要

稳定的β-二酮亚胺锗（II）氢化物 LGeH（1）[L=HC（CMeNAr）2，Ar=2,6-异丙基 2C6H3]与一氧化二氮、三甲基硅基叠氮化物、酮和炔烃的反应已被描述。1 与一氧化二氮反应生成锗（II）氢氧化物 LGeOH（2），与三甲基硅基叠氮化物在室温下在甲苯中生成锗（II）叠氮化物 LGeN3（3），还生成锗（IV）二酰胺 L'Ge（NHSiMe3）2（L'=CH{（CCH2）（CMe）（2,6-异丙基 2C6H3N）2}）（4）。酮（PhCOCF3，2-C4H3SCOCF3）和 1 生成了高收率的锗（II）烷氧基化物（5-6）。活性末端炔烃（HC[三重键]CCO2Me）和二取代炔烃（EtO2CC[三重键]CCO2Et）与 1 反应生成锗（II）取代的烯烃（乙烯基锗亚基）（7-8）。进一步反应，甲基锗（II）化合物 LGeMe（9）与三甲基硅基重氮甲烷反应生成锗（IV）酰胺 L'Ge（Me）NHN=CHSiMe3（10）。化合物 2-8 和 10 通过微量分析和多核 NMR 光谱学进行了表征。此外，化合物 3-6 和 8 通过 X 射线结构分析得到了证实。