Base-Free Iron Hydrosilylene Complexes via an α-Hydride Migration that Induces Spin Pairing,Journal of the American Chemical Society

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Base-Free Iron Hydrosilylene Complexes via an α-Hydride Migration that Induces Spin Pairing
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2018-03-12 , DOI: 10.1021/jacs.8b01185
Patrick W. Smith ₁ , T. Don Tilley ₁

Affiliation

Two new base-free hydrosilylene complexes of iron were synthesized using the novel starting material Cp*( iPr2MeP)FeMes. These Cp*( iPr2MeP)Fe(H)SiHR (R = DMP, Trip) complexes are in equilibrium with the corresponding iron silyl complexes, Cp*( iPr2MeP)FeSiH2R, which can be trapped and characterized for R = Trip. Unlike the Ru analogues, the Fe silylene complex with R = DMP is observed to undergo an intramolecular C-H activation involving formal addition of a benzylic C-H bond across the Fe-Si bond. This increased activity for bond activations is also observed for reactions with hydrogen, where Fe reacts faster than a Ru analog to form the hydrogenation product, Cp*( iPr2MeP)H2FeSiH2DMP.

中文翻译：

通过α-氢化物迁移诱导自旋配对的无碱铁氢化硅烷配合物

使用新型起始材料 Cp*(iPr2MeP)FeMes 合成了两种新的无碱氢化硅烯配合物。这些 Cp*( iPr2MeP)Fe(H)SiHR (R = DMP, Trip) 配合物与相应的铁甲硅烷基配合物 Cp*( iPr2MeP)FeSiH2R 处于平衡状态，可以将其捕获并表征为 R = Trip。与 Ru 类似物不同，观察到具有 R = DMP 的 Fe 亚甲硅烷基复合物经历分子内 CH 活化，包括在 Fe-Si 键上正式添加苄基 CH 键。在与氢的反应中也观察到这种增加的键活化活性，其中 Fe 比 Ru 类似物反应更快，形成氢化产物 Cp*( iPr2MeP)H2FeSiH2DMP。

更新日期：2018-03-12

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