Functionalization of a cyclo-P5 Ligand by Main-Group Element Nucleophiles
Functionalization of a cyclo-P5 Ligand by Main-Group Element Nucleophiles
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DOI：
10.1002/anie.201403581
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发表时间：
2014-07-14
影响因子：
16.6
通讯作者：
Scheer, Manfred
中科院分区：
文献类型：
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作者：
Maedl, Eric;Butovskii, Mikhail V.;Scheer, Manfred
通过 [Cp* Fe(eta(5)-P-5)] (1; Cp*=eta(5)-C5Me5) 与不同亲核试剂的反应，获得了前所未有的带有 eta(4)-P-5 环的官能化产物。使用LiCH2SiMe3和LiNMe2，分别形成单阴离子产物[Cp*Fe(eta(4)-P5CH2SiMe3)](-)和[Cp*Fe(eta(4)-P5NMe2)](-)。 1与NaNH2的反应导致形成三阴离子化合物[{Cp*Fe(eta(4)-P-5)}(2)N](3-)，而与LiPH2的反应产生[Cp*Fe(eta(4)-P5PH2)](-)作为主产物，并副产物{[Cp*Fe(eta(4)-P-5)](2)PH}(2-)。计算出的反应能量分布为不同产物的形成提供了理论依据。
Unprecedented functionalized products with an eta(4)-P-5 ring are obtained by the reaction of [Cp* Fe(eta(5)-P-5)] (1; Cp*=eta(5)-C5Me5) with different nucleophiles. With LiCH2SiMe3 and LiNMe2, the monoanionic products [Cp*Fe(eta(4)-P5CH2SiMe3)](-) and [Cp*Fe(eta(4)-P5NMe2)](-), respectively, are formed. The reaction of 1 with NaNH2 leads to the formation of the trianionic compound [{Cp*Fe(eta(4)-P-5)}(2)N](3-), whereas the reaction with LiPH2 yields [Cp*Fe(eta(4)-P5PH2)](-) as the main product, with {[Cp*Fe(eta(4)-P-5)](2)PH}(2-) as a byproduct. The calculated energy profile of the reactions provides a rationale for the formation of the different products.