Ligand-Induced Product Switching between 4-Methyl-1-pentene and 2-Methyl-1-pentene in Bis(imino)pyridine/V(III)-Catalyzed Propylene Dimerization: Cossee–Arlman Versus Metallacycle Mechanism,Organometallics

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Ligand-Induced Product Switching between 4-Methyl-1-pentene and 2-Methyl-1-pentene in Bis(imino)pyridine/V(III)-Catalyzed Propylene Dimerization: Cossee–Arlman Versus Metallacycle Mechanism
Organometallics ( IF 2.5 ) Pub Date : 2021-05-20 , DOI: 10.1021/acs.organomet.1c00167
Lin Liu ₁ , Zhen Liu ₁ , Ruihua Cheng ₁ , Xuelian He ₁ , Boping Liu ₂

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Ligand-induced product switching between 4-methyl-1-pentene (4M1P) and 2-methyl-1-pentene (2M1P) for propylene dimerization with a bis(imino)pyridine vanadium(III) catalytic system was investigated using the combined density functional theory and DLPNO-CCSD(T) method to determine which mechanism (metallacycle vs Cossee–Arlman) is most likely to be present. The calculations show that the Cossee–Arlman mechanism has low rate-determining energy barriers in comparison to the metallacycle mechanism. The NBO charge analysis supports that the electron-withdrawing/pushing substituents influence the process of the first propylene insertion, while the steric position of the ligand and vanadium affects the process of the second propylene insertion. The different substituents introduced to the backbone of the ligand changed the rate-determining step, which induced the switchable selectivity between 4M1P and 2M1P.

中文翻译：

双(亚氨基)吡啶/V(III)-催化丙烯二聚反应中4-甲基-1-戊烯和2-甲基-1-戊烯之间的配体诱导产物转换：Cossee-Arlman与金属环机制

使用组合密度泛函研究了 4-甲基-1-戊烯 (4M1P) 和 2-甲基-1-戊烯 (2M1P) 之间的配体诱导产物转换，用于丙烯与双（亚氨基）吡啶钒 (III) 催化体系的二聚反应理论和 DLPNO-CCSD(T) 方法来确定哪种机制（金属环与Cossee-Arlman）最有可能出现。计算表明，与金属循环机制相比，Cossee-Arlman 机制具有较低的速率决定能垒。NBO电荷分析支持吸电子/推电子取代基影响第一次丙烯插入的过程，而配体和钒的空间位置影响第二次丙烯插入的过程。引入配体骨架的不同取代基改变了速率决定步骤，从而诱导了 4M1P 和 2M1P 之间的可切换选择性。

更新日期：2021-06-14

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