在石墨中还原阳离子Ge II络合物[dimpyrGeCl] [GeCl 3 ](dimpyr = 2,6-(ArN = CMe)2 NC 5 H 3, Ar = 2,6 - i Pr 2 C 6 H 3)苯提供对空气敏感的深绿色Ge 0化合物,[dimpyrGe],其通过双(亚氨基)吡啶平台稳定。该化合物是不含卡宾或类胡萝卜素配体的零价14族元素络合物的第一个实例。该物种具有单重态基态。DFT研究表明,Ge孤对之一在亚胺的π*(CN)轨道上发生了部分离域化。这种离域作用导致Ge原子和亚胺氮原子之间具有部分多重键特征,这一事实得到X射线晶体学和IR光谱数据的支持。
在石墨中还原阳离子Ge II络合物[dimpyrGeCl] [GeCl 3 ](dimpyr = 2,6-(ArN = CMe)2 NC 5 H 3, Ar = 2,6 - i Pr 2 C 6 H 3)苯提供对空气敏感的深绿色Ge 0化合物,[dimpyrGe],其通过双(亚氨基)吡啶平台稳定。该化合物是不含卡宾或类胡萝卜素配体的零价14族元素络合物的第一个实例。该物种具有单重态基态。DFT研究表明,Ge孤对之一在亚胺的π*(CN)轨道上发生了部分离域化。这种离域作用导致Ge原子和亚胺氮原子之间具有部分多重键特征,这一事实得到X射线晶体学和IR光谱数据的支持。
Lewis Base Mediated Autoionization of GeCl<sub>2</sub>and SnCl<sub>2</sub>
作者:Amit Pratap Singh、Herbert W. Roesky、Elena Carl、Dietmar Stalke、Jean-Philippe Demers、Adam Lange
DOI:10.1021/ja300563g
日期:2012.3.14
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 center dot dioxane and SnCl2 in toluene gives compounds [(LB)(GeCl)-Cl-II](+)[(GeCl3)-Cl-II](-) (1) and [(LB)(SnCl)-Cl-II](+)[(SnCl3)-Cl-II](-) (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.