Facile proton-coupled electron transfer enabled by coordination-induced E–H bond weakening to boron
Facile proton-coupled electron transfer enabled by coordination-induced E–H bond weakening to boron
复制标题
通过配位诱导 E-H 键弱化至硼，实现轻松的质子耦合电子转移
DOI：
10.1039/d1cc02832d
复制
发表时间：
2021
影响因子：
4.9
通讯作者：
Ménard, Gabriel
中科院分区：
文献类型：
--
作者：
Wong, Anthony;Chakraborty, Arunavo;Bawari, Deependra;Wu, Guang;Dobrovetsky, Roman;Ménard, Gabriel
我们报道了芳基E-H（ArEH; E = N，O，S; Ar = Ph或C6 F5）或氨N-H键通过配位诱导的键弱化到络合物中的氧化还原活性硼中心（1−）而容易活化。在E-H键解离自由能（BDFE）的大幅下降，观察基板的协调，使随后的容易质子耦合电子转移（PCET）。实验确定了在配位时H2 N-H BDFE中的>50 kcal mol−1的下降。
We report the facile activation of aryl E–H (ArEH; E = N, O, S; Ar = Ph or C6F5) or ammonia N–H bonds via coordination-induced bond weakening to a redox-active boron center in the complex, (1−). Substantial decreases in E–H bond dissociation free energies (BDFEs) are observed upon substrate coordination, enabling subsequent facile proton-coupled electron transfer (PCET). A drop of >50 kcal mol−1 in H2N–H BDFE upon coordination was experimentally determined.