Yue Yunfan, Ma Tian, Qi Hexiang, Zhao Yaqi, Shi Xiaofan, Tang Yanhui, Pu Min, Lei Ming
State Key Laboratory of Chemical Resource Engineering, Institute of Computational Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing, 100029, China.
School of Materials Design and Engineering, Beijing Institute of Fashion Technology, Beijing, 100029, China.
Phys Chem Chem Phys. 2023 Oct 18;25(40):27829-27835. doi: 10.1039/d3cp03217e.
Herein, a new series of bowl-shaped quadridentate ligands with a Si-N-Si-C-Si-C six-membered ring core and their manganese catalysts were designed using the density functional theory (DFT) method for the hydrogenation of unsaturated CX (XN, O) bonds. The frameworks of these ligands named by LYG (LYG = P(R)CHSi(CH)(CH)NSi(CH)(CHSi(CH)CHP(R))CHP(R)) have a Si-N-Si-C-Si-C six-membered ring core at the bottom of the bowl structure and each Si atom links with one phosphorus arm (-CHPR). The Mn catalyst Mn(CO)-LYG was constructed to catalyze the hydrogenation of CO/CN bonds. The calculated results indicate that due to the bowl-shaped structure of LYG quadridentate ligands, these Mn catalysts could be advantageous not only in the tuneup of catalytic activity and stereoselectivity by modifying three phosphorus arms but also in the homogeneous catalyst immobilization by linking with the Si-N-Si-C-Si-C six-membered ring core using different supports. This work might provide theoretical insights to design new framework transition-metal catalysts for the hydrogenation of CX bonds.
在此，利用密度泛函理论（DFT）方法设计了一系列具有Si-N-Si-C-Si-C六元环核心的新型碗状四齿配体及其锰催化剂，用于不饱和CX（XN、O）键的氢化反应。这些名为LYG的配体（LYG = P(R)CHSi(CH)(CH)NSi(CH)(CHSi(CH)CHP(R))CHP(R)）的骨架在碗状结构底部具有一个Si-N-Si-C-Si-C六元环核心，且每个Si原子与一个磷臂（-CHPR）相连。构建了锰催化剂Mn(CO)-LYG以催化CO/CN键的氢化反应。计算结果表明，由于LYG四齿配体的碗状结构，这些锰催化剂不仅在通过修饰三个磷臂来调节催化活性和立体选择性方面具有优势，而且在使用不同载体与Si-N-Si-C-Si-C六元环核心连接以实现均相催化剂固定化方面也具有优势。这项工作可能为设计用于CX键氢化反应的新型骨架过渡金属催化剂提供理论见解。
