无卤氧化锗的转化：（DTBC）Ge[Py（CN）]（n = 0…2）配合物中的电化学还原与络合反应的比较。

Halogen-free GeO conversion: electrochemical reduction vs. complexation in (DTBC)Ge[Py(CN)] (n = 0…2) complexes.

机构信息

N.D. Zelinsky Institute of Organic Chemistry RAS, Moscow, Russia.

出版信息

Dalton Trans. 2018 Dec 4;47(47):17127-17133. doi: 10.1039/c8dt03397h.

Abstract

3,5-di-tert-Butylcatecholate (DTBC) germanium complexes (DTBC)2Ge[Py(CN)n]2 (n = 0…2) have been synthesized from GeO2, 3,5-di-tert-butylcatechol and cyano-substituted pyridines Py(CN)n and characterized by elemental analysis, NMR, IR and UV-VIS spectroscopy. The structure of 1 (with 4-cyanopyridine) has been determined by X-ray single crystal analysis. UV-VIS spectra have shown that these complexes are stable in CH3CN, toluene and CH2Cl2 solutions; in contrast, they are rapidly decomposed by dimethylformamide and tetrahydrofuran. Complexes 1 and 2 (with 4-cyano and 3-cyanopyridine) are electrochemically reducible in toluene/1 M Bu4NPF6 at E = -1.3…-1.7 V vs. AgCl. The quantum-chemical study of these complexes is in accordance with the unsuccessful attempts to obtain analogous derivatives with 2-cyanopyridine and 2,6-dicyanopyridine.

摘要

3,5-二叔丁基儿茶酚锗（DTBC）配合物（DTBC）2Ge[Py（CN）n]2（n = 0…2）已通过 GeO2、3,5-二叔丁基儿茶酚和取代氰基吡啶 Py（CN）n合成，并通过元素分析、NMR、IR 和 UV-VIS 光谱进行了表征。1（带有 4-氰基吡啶）的结构已通过 X 射线单晶分析确定。UV-VIS 光谱表明，这些配合物在 CH3CN、甲苯和 CH2Cl2 溶液中稳定；相比之下，它们在二甲基甲酰胺和四氢呋喃中迅速分解。配合物 1 和 2（带有 4-氰基和 3-氰基吡啶）在甲苯/1 M Bu4NPF6 中可在 E = -1.3…-1.7 V 相对于 AgCl 电化学还原。对这些配合物的量子化学研究与用 2-氰基吡啶和 2,6-二氰基吡啶获得类似衍生物的不成功尝试相符。