Selective H/D Exchange of Pyridines and Alkylarenes with D2 Enabled by a Heterometallic Mg-Ni-Mg Polyhydride Complex
Yanping Cai1,2, Mengwei Wang1,2, Yueyue Yang1,2, Xin Xu1,2（徐信）*
1Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China
2State Key Laboratory of Bioinspired Interfacial Materials Science, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China
Inorg. Chem. 2025, 64, 14598
Abstract: Heterometallic polyhydride complexes containing main-group metals and transition metals have attracted much attention due to their versatile MHn units and potential metal–metal synergies for molecular transformation. In this work, we report that a heterometallic Mg–Ni–Mg polyhydride complex [(LMg)2NiH4] {L = [(DippNCMe)2CH]−, Dipp = 2,6-iPr2C6H3} is able to catalyze the selective H/D exchange of ortho C(sp2)–H bonds of pyridine derivatives with D2 to obtain deuterium-labeled compounds with high isotopic incorporation. Moreover, benzylic C(sp3)–H bonds are also successfully labeled using D2 in the presence of [(LMg)2NiH4]. Pharmaceuticals with high isotopic incorporation have also been achieved with this catalytic system. Stoichiometric reactions of [(LMg)2NiH4] with pyridines yield the Mg-Ni cooperativemono- andbis-ortho C-H bond activation complexes, i.e., trihydride [(LMg)2NiH3(NC5H4R)(NC5H3R)] (R=Ph, Et) and dihydride [(LMg)2NiH2(NC5H3Ph)2], which are considered as active intermediates in the catalytic process.
Article information: https://doi.org/10.1021/acs.inorgchem.5c02150
