LGeCl(L = CH [C(Me)N(Ar)] 2 ; Ar = 2,6- i Pr 2 C 6 H 3)与KO t Bu或LiR(R = 2-噻吩基,N(H))的反应Ar,PPh 2)得到锗(II)化合物LGeR [R = O t Bu(1),2-噻吩基(2),N(H)Ar(3),PPh 2(4)]。用锂还原(2-噻吩基)2 PCl得到二膦[(2-噻吩基)2 P] 2(5)。用LiAlH 4或KHB处理(2-噻吩基)2 PClt Bu 3导致(2-噻吩基)2 PH(6)的形成。NHC辅助的LGeCl和6的反应导致LGeP(2-噻吩基)2(7)的分离。这是第一个将NHC用于从具有PH和Ge-Cl键的化合物中去除HCl的例子。通过元素分析,NMR和IR光谱以及单晶X射线结构测定来表征所有固体产物。
A Cyclopentadienide Analogue Containing Divalent Germanium and a Heavy Cyclobutadiene-like Dianion with an Unusual Ge<sub>4</sub> Core
作者:Wenyuan Wang、Shenglai Yao、Christoph van Wüllen、Matthias Driess
DOI:10.1021/ja802502b
日期:2008.7.1
The first isolable cyclogermylidenide salt 2 has been synthesized and isolated by facile dehalogenation of the N-heterocyclic chlorogermylene 1 with elemental potassium in ether and isolated in the form of yellow crystals in 33% yield. Single-crystal X-ray diffraction analysis revealed that 2 crystallizes as a dimeric half-sandwich complex of aromatic C3NGe rings interconnected via intermolecular Ge(II) K dative bonds. Its yield can be improved up to 42% by gentle reduction of 1 (or its related GeCl3 complex 8) using potassium graphite. Additionally, the remarkable K2Ge4 cluster compound 9 has been isolated as a side product which consists of an unusual dianionic Ge-4 core with parallelogram configuration and pronounced aromaticity as indicated by highly negative NICS values.