Synthesis, structure, and catalytic properties of heteroelement carbene tungsten complexes Ph3ECH=W(OBu-t)2(OPh)2 (E = Si, Ge)
摘要:
Novel silicon- and germanium-containing tungsten complexes Ph3ECH=W(OBu-t)(2)(OPh)(2) were synthesized by the reaction of carbyne derivatives Ph3ECa parts per thousand W(OBu-t)(3) (E = Si, Ge) with phenol and isolated in high yields. Their structure was determined by X-ray diffraction. Individual complexes do not exhibit catalytic activity, whereas in the presence of AlBr3 they initiate metathesis polymerization of cyclooctene.
Reactions of silicon-, germanium- and tin-containing carbene complexes of tungsten Ph3E–CW(OBut)3 (E=Si, Ge, Sn) with hydrogen chloride: crystal structures of carbene complexes Ph3E–CHWCl2(OBut)2 (E=Si, Ge)
and -tin-containing carbenecomplexes of tungsten of the type Ph3E–CHWCl2(OBut)2 (E=Si, Ge, Sn) have been prepared by the reaction of heteroelement-containing carbenecomplexes of tungsten Ph3E–CW(OBut)3 (E=Si, Ge, Sn) with hydrogenchloride. The tin-containing carbenecomplex was identified in solution by 1H NMR spectroscopy. Silicon- and germanium-containing carbenecomplexes were isolated in high
通过含杂元素的反应,制备了新型的有机硅,Ph 3 E–CHWCl 2(OBu t)2(E = Si,Ge,Sn)的钨的含锗和含锡的卡宾配合物。钨Ph 3 E–CW(OBu t)3(E = Si,Ge,Sn)与氯化氢的卡宾配合物。通过1 H NMR光谱鉴定溶液中的含锡卡宾配合物。高产率地分离出含硅和锗的卡宾配合物,为结晶固体,并通过元素分析,IR,1 H NMR,13 C NMR和29进行表征Si NMR光谱和X射线衍射研究。化合物中W原子的几何形状可以描述为扭曲的方形金字塔。
Synthesis and structures of germanium-containing tungsten carbyne complexes Ph3gec≡w(ch2but)3 and Ph3GeC≡W(CH2SiMe3)3
作者:A. V. Safronova、L. N. Bochkarev、N. E. Stolyarova、I. K. Grigorieva、I. P. Malysheva、G. V. Basova、G. K. Fukin、E. V. Baranov、Yu. A. Kurskii、G. A. Abakumov
DOI:10.1007/s11172-006-0240-0
日期:2006.2
New germanium-containing tungsten carbyne complexes Ph3GeC≡W(CH2R)3 (R = But or SiMe3) were synthesized by the reaction of the alkoxy derivative Ph3GeC≡W(OBut)3 with alkyllithium reagents RCH2Li. The new compounds were isolated in individual form as crystals in 95 and 90% yields, respectively, and were characterized by elemental analysis, 1H and 13C NMR spectroscopy, and X-ray diffraction. X-ray diffraction study showed that the coordination environment of the W and Ge atoms in the Ph3GeC≡ W(CH2But)3 and Ph3GeC≡W(CH2SiMe3)3 complexes can be described as a distorted tetrahedron.
通过烷氧基衍生物 Ph3GeC≡W(OBut)3 与烷基锂试剂 RCH2Li 的反应,合成了新的含锗羰基络合物 Ph3GeC≡W(CH2R)3 (R = But 或 SiMe3)。通过元素分析、1H 和 13C NMR 光谱以及 X 射线衍射,对这些新化合物进行了表征。X 射线衍射研究表明,Ph3GeC≡W(CH2But)3 和 Ph3GeC≡W(CH2SiMe3)3 复合物中 W 原子和 Ge 原子的配位环境可以描述为一个扭曲的四面体。