Synthesis, structures and reactivity of novel germanium(II) aryloxide and arylsulfide complexes
Synthesis, structures and reactivity of novel germanium(II) aryloxide and arylsulfide complexes
复制标题
新型芳氧基锗(II)和芳硫醚配合物的合成、结构和反应性
DOI：
10.1039/b211077f
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发表时间：
2003
影响因子：
4
通讯作者：
I. Rothwell
中科院分区：
文献类型：
--
作者：
C. S. Weinert;A. E. Fenwick;P. Fanwick;I. Rothwell
Ge[N(SiMe_3)_2]_2与取代苯酚发生质子解反应生成新的锗(II)芳氧基配合物[Ge(Oar)_2]_n
(N)
=2，Aro=OC6H2 Me3-2，4，6 1或OC6H3iPr2-2，6 2；n
=1，Aro=OC6H3Ph2-2，6 3或OC6HPh4-2，3，5，6 4)。用X射线衍射法测定了1-4的固态结构，并与它们的光谱性质进行了比较。化合物1和2含有桥联芳氧基配体，锗原子周围的环境是金字塔形的。化合物1与苯并苯反应生成五配位锗配合物[Ge(OC6H2Me3-2，4，6)(O2C2Ph2)(O2C2HPh2)]
5，而化合物4与同一试剂反应得到[Ge(OC6HPh4-2，3，5，6)2(O2C2Ph2)]
6.测定了5和6的X-射线晶体结构。化合物4还与CH3I发生氧化加成反应，生成锗[Ge(OC6HPh4-2，3，5，6)2(Me)(I)]。
(7)。一种新的芳基硫化锗[HGe(SC6H_2iPr3-2，4，6)3]
在Ge[N(SiMe_3)_2]_2与HSC_6H_2iPr3-2，4，6反应中分离得到一个化合物，经核磁共振波谱和X-射线晶体结构确证。
The protonolysis reactions between Ge[N(SiMe3)2]2 and substituted phenols give rise to new germanium(II) aryloxide complexes [Ge(OAr)2]n
(n
= 2, ArO = OC6H2Me3-2,4,6 1 or OC6H3iPr2-2,6 2; n
= 1, ArO = OC6H3Ph2-2,6 3 or OC6HPh4-2,3,5,6 4). The solid state structures of 1–4 have been determined by X-ray diffraction and compared to their spectroscopic properties. Compounds 1 and 2 contain bridging aryloxide ligands and the environment about the germanium atoms is pyramidal. Compound 1 reacts with benzil to yield a five-coordinate germanium complex [Ge(OC6H2Me3-2,4,6)(O2C2Ph2)(O2C2HPh2)]
5, while compound 4 reacts with the same reagent to give [Ge(OC6HPh4-2,3,5,6)2(O2C2Ph2)]
6. The X-ray crystal structures of 5 and 6 have also been determined. Compound 4 also undergoes an oxidative addition reaction with CH3I to yield the germane [Ge(OC6HPh4-2,3,5,6)2(Me)(I)]
(7). A novel arylsulfidegermane, [HGe(SC6H2iPr3-2,4,6)3]
8, was isolated in the reaction between Ge[N(SiMe3)2]2 and HSC6H2iPr3-2,4,6 and was characterized by NMR spectroscopy and an X-ray crystal structure.