Citation: LÜ Ling-Ling, ZHU Yuan-Cheng, ZUO Guo-Fang, YUAN Kun, WANG Yong-Cheng. Theoretical Investigation on the Multi-State Reaction Mechanism for the Propene Catalyzed by Non-Heme Ferric-Superoxo Species[J]. Chinese Journal of Inorganic Chemistry, ;2017, 33(2): 329-339. doi: 10.11862/CJIC.2017.028 shu

Theoretical Investigation on the Multi-State Reaction Mechanism for the Propene Catalyzed by Non-Heme Ferric-Superoxo Species

1.
College of Chemical Engineering and Technology, Tianshui Normal University, TianShui, Gansu 741001, China
2.
College of Chemistry and Chemical Engineering, Northwest Normal University, LanZhou, 730070, China

Corresponding author: LÜ Ling-Ling, lvling002@163.com
Received Date: 4 February 2016
Revised Date: 3 December 2016

Figures(8)

The multi-state reaction mechanism for the propene catalyzed by non-heme ferric-superoxo model complex has been investigated at the DFT-B3LYP level. The calculations show that non-heme ferric-superoxo complex can be considered as effective oxidants in hydrogen atom abstraction reaction (single-state-reactivity), for which we find a lower barrier of ΔG^≠=65.6 kJ·mol^-1 on the septet spin state surface. Single-state-reactivity is possibly due to the recently proposed exchange-enhanced reactivity (EER)principle with larger exchange stabilization of the Fe center. For the O-O bond activated step, we computed the spin-orbit coupling (SOC)constants of the septet, S₁ and quintet, Q₀ state at the crossing region and found it to be 2.26 and 2.19 cm^-1 at the CASSCF (10, 8)/6-31+G (d)//TZVP levels, respectively. Orbital analysis show that two spin orbitals have the same spatial component in their wave functions (π_sub^*), therefore, the S=3 surface cannot effectively intersystem cross to the S=2 surface through the SOC interactions, and the intersystem crossing is possibly occurred at the exit stage of the reaction.
- non-heme ferric-superoxo,
- multi-state reaction mechanism,
- intersystem crossing,
- spin-orbit coupling
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沈阳化工大学材料科学与工程学院沈阳 110142