摘要/Abstract

白磷直接合成有机膦化合物具有重要的科学意义，因为其不仅避免了磷化工生产过程中产生的大量污染，而且可以用于合成许多结构新颖的含磷化合物.从镥杂环戊二烯与白磷的反应中分离并表征了一例新颖的三核稀土金属配合物[{（η⁵-C₅Me₅）LuCl}₃（THF）P₆][Li（THF）₄].该配合物具有一个六磷杂并环[3.1.0]己烷四负离子配体，相比于其他已知的六磷杂己烷类配体，该配体目前仍未被报道.X射线单晶衍射实验表明，该六磷杂并环[3.1.0]己烷四负离子配体采取的船式构象，与三个稀土金属分别以η¹，η³，η³的方式配位，形成一个结构新颖的[P₆Lu₃]笼状结构.密度泛函理论（DFT）计算表明，该化合物在其两侧分别有一个三中心两电子键.
关键词: 多膦配体, 白磷活化, 稀土金属配合物
Direct synthesis of organophosphorus compounds from white phosphorus (P₄) is of great significance because this process avoids the industry pollution synthetic methods and provides the possibilities for many novel phosphorus-containing compounds. A trinuclear rare-earth metal complex[{(η⁵-C₅Me₅)LuCl}₃(THF)P₆] [Li(THF)₄] from lutetacyclopentadiene mediated P₄ functionalization was isolated and characterized. This novel complex contains a bicyclo[3.1.0]-P₆^4- ligand which is an unreported type. X-ray diffraction analysis shows that the bicyclo[3.1.0]-P₆^4- ligand adopts a boat-like conformation. Three lutetium atoms coordinate to this ligand in η¹, η³, η³ mode, respectively, and a novel[P₆Lu₃] cage has been formed. Density functional theory (DFT) calculations indicate that there are two three-center two-electron bonds.
Key words: polyphosphorus ligand, white phosphorus activation, rare-earth-metal complex


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