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Reaction Mechanism and Kinetics study on Addition of CCl 4 to 1‐hexene Catalyzed by Mo‐Mo Quintuply‐bond
Author(s) -
Kang Lixia,
Huo Suhong,
Meng Lingpeng,
Li Xiaoyan
Publication year - 2020
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.5726
Subject(s) - chemistry , catalysis , 1 hexene , hexene , pyridine , redox , transition metal , metal , medicinal chemistry , reaction mechanism , density functional theory , photochemistry , computational chemistry , inorganic chemistry , organic chemistry , ethylene
Transition metal‐catalyzed atom transfer radical addition (ATRA) reactions are an effective and versatile strategy for constructing carbon–carbon bonds in organic synthesis. Typically, the metal center in this metal‐assisted radical transformation undergoes a reversible redox process. In this work, a quintuply‐bonded dinuclear complex, Mo 2 (N ∧ N) 2 {N ∧ N = μ‐κ 2 ‐CH[N(2,6‐ i Pr 2 C 6 H 3 )] 2 }, has been investigated as potential catalyst for radical addition of CCl 4 to 1‐hexene by performing density functional theory (DFT) calculations. The study shows that the Mo 2 (N ∧ N) 2 ‐mediated radical addition reaction is computationally predicted to occur with acceptable activation energies, indicating that the Mo‐Mo quintuple bond can be applied as an effective catalyst for this transformation under mild conditions. The whole reaction involves 3 steps, two of which are metal‐mediated. Firstly, the C‐Cl bond activiation catalyzed by Mo 2 (N ∧ N) 2 to obtain Mo 2 (N ∧ N) 2 Cl and ·CCl 3 radical; Then the ·CCl 3 radical interacts with 1‐hexene to get an addition, the addition product reacts with the Mo 2 (N ∧ N) 2 Cl to get the last product and regenerate the catalyst Mo 2 (N ∧ N) 2 . Both the thermodynamic and kinetic study show that the second step is the rate‐determine step. When coordinating solvent pyridine is added to the catalytic reaction, the reaction is suppressed due to their high energies barriers, which is consistent with experimental results.