Synthesis of Cationic Silaamidinate Germylenes and Stannylenes and the Catalytic Application for Hydroboration of Pyridines

作者：Chaopeng Hu, Jianying Zhang, Hao Yang, Lulu Guo, Chunming Cui · 发表于：Inorganic Chemistry · 年份：2021 · DOI：10.1021/acs.inorgchem.1c01314 · 被引用次数：14 · 研究领域：Synthesis and characterization of novel inorganic/organometallic compounds、Organoboron and organosilicon chemistry、Coordination Chemistry and Organometallics

The N-heterocyclic germylenes and stannylenes LSi(NAr) 2 EX (L = PhC(N t Bu) 2, Ar = 2,6- i Pr 2 C 6 H 3; E = Ge, Sn; X = Cl, CF 3 SO 3, BPh 4 ) supported by the bulky silaamidinate ligand [LSi(NAr) 2 ] − have been synthesized and fully characterized. The germylene triflate LSi(NAr) 2 GeOTf ( 3b ) and dimeric borate [LSi(NAr) 2 Ge] 2 ClBPh 4 ( 3a ) enabled highly regio- and chemoselective catalytic hydroboration of pyridines and may represent the most active catalytic system for the transformation. DFT calculations disclosed that the cationic germylene [LSi(NAr) 2 Ge] + with a low-lying LUMO energy initiated the catalytic process. In contrast, the analogous amidinate germylene triflates are almost inactive, indicating the silaamidinate ligand is essential for the stabilization of cationic species.