Synthesis, spectroscopic and structural systematics of complexes of germanium(IV) halides (GeX4, X = F, Cl, Br or I) with phosphane oxides and related oxygen donor ligands
Synthesis, spectroscopic and structural systematics of complexes of germanium(IV) halides (GeX4, X = F, Cl, Br or I) with phosphane oxides and related oxygen donor ligands
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DOI：
10.1002/ejic.200700233
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发表时间：
2007-06-01
影响因子：
2.3
通讯作者：
Zhang, Wenjian
中科院分区：
文献类型：
--
作者：
Cheng, Fei;Davis, Martin F.;Zhang, Wenjian
合成了第一系列卤化锗膦氧化物配合物，包括反式[GeF4(R3PO)(2)](R=Me，Et或Ph)，反式[GeCl4(Et3PO)(2)]，Fac[GeCl3(Me3PO)(3)](2)[GeCl6]和顺式[GeX2(Me3PO)(4)]X-2(X=Cl或Br)，并用IR和多核核磁共振(H-1，F-19{H-1和P-31{H-1})进行了表征。描述了上述化合物的晶体结构(反式[GeCl4(Et3PO)(2)]除外)。值得注意的是，在温和的条件下，Me3PO取代了GeX4(X=Cl，Br)上的卤化物配体，形成了上述阳离子物种。Ph3AsO生成反式[GeF4(Ph3AsO)(2)]，而Ph3AsO或Me3AsO与GeCl4反应生成相应的R3AsCl2。文中还描述了配合物[GeF4(MeCN)(2)]、[GeF4(THF)(2)]和[GeF4(MeOCH2CH2OMe)]，并测定了GeX4的相对Lewis酸度。
The first series of phosphane oxide complexes of germanium(IV) halides have been prepared, including trans[GeF4(R3PO)(2)] (R = Me, Et or Ph), trans-[GeCl4(Et3PO)(2)], fac[GeCl3(Me3PO)(3)](2)[GeCl6] and cis-[GeX2(Me3PO)(4)]X-2 (X = Cl or Br) and characterised by IR and multinuclear NMR (H-1, F-19{H-1} and P-31{H-1}) spectroscopy. Crystal structures of all the above (except trans-[GeCl4(Et3PO)(2)]) are described. Remarkably, under mild conditions Me3PO displaces halide ligands from GeX4 (X = Cl, Br) to form the cationic species above. Ph3AsO forms trans- [GeF4(Ph3AsO)(2)], but reaction of Ph3AsO or Me3AsO with GeCl4 leads to the corresponding R3AsCl2. The complexes [GeF4(MeCN)(2)], [GeF4(thf)(2)] and [GeF4(MeOCH2CH2OMe)] are also described and the relative Lewis acidities of GeX4 established.