Ambireactive (R3 P)2 BH2 Groups Facilitating Temperature-Switchable Bond Activation by an Iron Complex.
Ambireactive (R3 P)2 BH2 Groups Facilitating Temperature-Switchable Bond Activation by an Iron Complex.
复制标题
DOI：
10.1002/chem.201704018
复制
发表时间：
2018-01
期刊：
影响因子：
--
通讯作者：
Lisa Vondung;L. Sattler;R. Langer
中科院分区：
文献类型：
--
作者：
Lisa Vondung;L. Sattler;R. Langer
一个铁钳配合物含有半不稳定的（R3 P）2 BH 2基团表现出温度可切换的反应模式：可逆的B-H活化伴随着P-B键裂解观察到在室温下。低于4 °C，分子内和分子间C-H活化途径变得更快和更占主导地位。机理研究表明，（R3 P）2BH 2基团的不稳定性和σ-键合络合物的放热形成是可转换键活化的原因.最后，一个协议的铁催化的H/D-交换的有机溶剂在没有氧化剂的情况下已经开发。
An iron pincer complex containing a hemi-labile (R3 P)2 BH2 group exhibits temperature-switchable reactivity patterns: a reversible B-H activation concomitant with a P-B bond cleavage is observed at room temperature. Below 4 °C, intra- and intermolecular C-H activation pathways are becoming faster and more dominant. Mechanistic investigations reveal that the lability of the (R3 P)2 BH2 group in combination with the exothermic formation of σ-bonded complexes are responsible for the switchable bond activation. Finally, a protocol for an iron-catalyzed H/D-exchange of organic solvents in the absence of oxidants has been developed.