当前位置: X-MOL 学术J. Comput. Chem. › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Insights into the electronic structure and mechanism of norcarane hydroxylation by OxoMn(V) porphyrin complexes: A density functional theory study
Journal of Computational Chemistry ( IF 3 ) Pub Date : 2021-08-06 , DOI: 10.1002/jcc.26715
Zhifeng Ma 1 , Naoki Nakatani 1 , Masahiko Hada 1
Affiliation  

Norcarane hydroxylation by neutral [PorMn(V)O-L] (L═OH, F) and cationic [PorMn(V)O-L]+ (L═H2O, imidazole) oxoMn(V) porphyrin complex models has been investigated by density functional theory calculations to better understand the reaction mechanism and electronic structure. We found that the energy barriers of norcarane hydroxylation by cationic oxoMn(V) porphyrin complexes are lower than those by neutral oxoMn(V) porphyrin complexes. This indicates that cationic oxoMn(V) porphyrin complexes enhance norcarane hydroxylation compared with neutral oxoMn(V) porphyrin complexes. According to electronic structure analysis, in the C─H activation step, electron transfer occurs through initial interaction between the σCH and rich-oxygen π(Mn═O) orbitals to form real donor orbitals, followed by transfer to the acceptor π*(Mn═O) orbitals. Moreover, single electron shifts from norcarane (CH) to Mn atom during C─H activation. The positive charge of the cationic complex stabilizes the acceptor orbital more than the donor orbital, reducing the energy gap between these orbitals, thus lowering the reaction barrier.

中文翻译:

OxoMn(V) 卟啉配合物对去甲卡烷羟基化的电子结构和机理的洞察:密度泛函理论研究

已通过中性 [PorMn(V)OL] (L=OH - , F - ) 和阳离子 [PorMn(V)OL] + (L = H 2 O, 咪唑) oxoMn(V) 卟啉络合物模型研究了去甲烷羟基化密度泛函理论计算以更好地了解反应机理和电子结构。我们发现阳离子 oxoMn(V) 卟啉复合物的去甲卡烷羟基化的能垒低于中性 oxoMn(V) 卟啉复合物的能垒。这表明与中性 oxoMn(V) 卟啉复合物相比,阳离子 oxoMn(V) 卟啉复合物增强了去甲烷羟基化。根据电子结构分析,在 C─H 激活步骤中,电子转移通过 σ CH之间的初始相互作用发生和富氧 π(Mn=O) 轨道形成真正的供体轨道,然后转移到受体 π*(Mn=O) 轨道。此外,在 C─H 活化过程中,单电子从降甲烷 (CH) 转移到 Mn 原子。阳离子络合物的正电荷比供体轨道更稳定受体轨道,减少这些轨道之间的能隙,从而降低反应势垒。
更新日期:2021-08-27
down
wechat
bug