Complexes with a Metal Phosphorus Triple Bond – a Novel Class of Highly Reactive Compounds
Complexes with a Metal Phosphorus Triple Bond – a Novel Class of Highly Reactive Compounds
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具有金属磷三键的配合物——一类新型的高反应性化合物
DOI：
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发表时间：
2001
期刊：
影响因子：
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通讯作者：
E. Leiner
中科院分区：
文献类型：
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作者：
M. Scheer;Peter Kramkowski;M. Schiffer;Brian P. Johnson;E. Leiner
通过亚膦配合物[Cp*P{W(CO)5}2]中P原子上的Cp*迁移到过渡金属上的→5配位，获得了一种新的高活性磷络合物中间体[Lnm=PσM‘(CO)5](M’=Cr，W).因此，这些化合物显示出很高的“侧面”反应活性。它们与磷杂炔、炔烃和腈的反应行为导致了新型偏磷杂环的合成。此外，使用相应的类似物[Cp*As{W(CO)5}2]通过热分解反应生成四核钨簇合物，这表明除了形成三键中间体[Cp*(CO)2W[As→W(CO)5]外，还存在第二个消除了Cp*的中间体[As{W(CO)5}2]。
A novel approach to highly reactive phosphido complex intermediates of the type [LnM=P→M′(CO)5] (M′ = Cr, W) is achieved via the Cp* migration from a σ-bound situation at a P atom in a phosphinidene complex [Cp*P{W(CO)5}2] to the η5-coordination at the transition metal. Consequently those compounds show a high “side-on” reactivity. Their reaction behavior with phosphaalkynes, alkynes and nitriles leads to novel metala-phosphaheterocycles. Furthermore, the use of the corresponding As analogue [Cp*As{W(CO)5}2] yields via thermolysis reaction the tetranuclear tungsten clusters, which indicate besides the formation of the triple bond intermediate [Cp*(CO)2W[As→W(CO)5] the occurrence of a second Cp* eliminated intermediate [As{W(CO)5}2].