Lewis Base Mediated Autoionization of GeCl2 and SnCl2

Cationic and anionic species of heavier low-valent group 14 elements are intriguing targets in main group chemistry due to their synthetic potential and industrial applications. In the present study, we describe the synthesis of cationic (MCl+) and anionic (MCl3–) species of heavier low-valent group 14 elements of germanium­(II) and tin­(II) by using the substituted Schiff base 2,6-diacetylpyridinebis­(2,6-diisopropylanil) as Lewis base (LB). Treatment of LB with 2 equiv of GeCl2·dioxane and SnCl2 in toluene gives compounds [(LB)­GeIICl]+[GeIICl3]− (1) and [(LB)­SnIICl]+[SnIICl3]− (2), respectively, which possess each a low-valent cation and an anion. Compounds 1 and 2 are well characterized with various spectroscopic methods and single crystal X-ray structural analysis.第14族重低氧化态元素的阳离子与阴离子物种，凭借其合成潜力与工业应用价值，成为主族化学领域极具研究价值的目标。本研究中，我们以取代希夫碱2,6-二乙酰吡啶双(2,6-二异丙基苯胺)作为路易斯碱（Lewis base, LB），成功合成了锗(II)与锡(II)这两类第14族重低氧化态元素的阳离子型（MCl+）与阴离子型（MCl3–）物种。将路易斯碱LB与2当量的二氧六环合氯化锗(II)（GeCl2·dioxane）、氯化锡(II)分别在甲苯中反应，可分别得到化合物[(LB)GeIICl]+[GeIICl3]−（1）与[(LB)SnIICl]+[SnIICl3]−（2），二者均各自包含一个低氧化态阳离子与一个阴离子。我们通过多种光谱学方法与单晶X射线结构分析，对化合物1与2进行了充分的结构表征。