What factors influence the reactivity of C-H hydroxylation and C=C epoxidation by [Fe(IV)(L(ax))(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)(O)](n+).
Density functional theory is used to investigate geometric structures and mechanisms for hydroxylation and epoxidation from propene for four non-heme iron complexes, [Fe(IV)(L(ax))(TMC)(O)](n+), which are the inverted isomers of [Fe(IV)(O)(TMC)(Lax)](n+) (Lax = acetonitrile (AN), monoanionic trifluoroacetate (TF), azide (N3), thiolate (SR)). The Fe(IV)O unit is found to be sterically less hindered in [Fe(IV)(L(ax))(TMC)(O)](n+) than that in [Fe(IV)(O)(TMC)(L(ax))](n+). Becke, three-parameter, Lee-Yang-Parr (B3LYP) calculations show that hydroxylation and epoxidation proceed via a two-state-reactivity on competing triplet and quintet spin surfaces; and the reactions have been invariably mediated by the S = 2 state. The reaction pathways computed reveal that 2-AN is the most reactive in the four [Fe(IV)(L(ax))(TMC)(O)](n+) complexes; along the reaction pathway, the axial ligand moves away from the iron center, and thus, the energy of the LUMO decreases. The anionic axial ligand, which is more electron releasing than neutral AN, shows a strong overlap of iron orbitals. Thus, the anionic ligand does not move away from the iron center. The H-abstraction is affected by the tunneling contribution, the more electron donation power of the axial ligand, the more effect of the tunneling contribution. Adding the tunneling correction, the relative reactivity of the hydroxylation follows the trend: 2-AN > 2-SR ≈ 2-N3 > 2-TF. However, for the epoxidation, the reactivity is in the following order of 2-AN > 2-TF > 2-N3 > 2-SR. Except for 2-AN, 2-X (L(ax) = TF, N3, SR) complexes chemoselectively hydroxylate even in the presence of a C=C double bond.
School of Biological Engineering, Dalian Polytechnic University, Dalian, 116034, China. wangyi@dlpu.edu.cn.
Wang
W
Yi
School of Biological Engineering, Dalian Polytechnic University, Dalian, 116034, China.
Liu
L
Yuan
Department of Physics, Dalian Maritime University, 1 Linghai Road, Dalian, 116026, China.
Yang
Y
Kun
School of Biological Engineering, Dalian Polytechnic University, Dalian, 116034, China.
He
H
Zhengwen
School of Biological Engineering, Dalian Polytechnic University, Dalian, 116034, China.
Tian
T
Jing
School of Biological Engineering, Dalian Polytechnic University, Dalian, 116034, China.
Fei
F
Xu
School of Biological Engineering, Dalian Polytechnic University, Dalian, 116034, China.
Guo
G
Hong
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000, China. wangyong@licp.cas.cn.
Wang
W
Yong
D000475:Alkenes / Q000737:chemistry; D003198:Computer Simulation; D056831:Coordination Complexes / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry*; D006900:Hydroxylation; D007501:Iron / Q000737:chemistry*
D000475:Alkenes; D056831:Coordination Complexes; D004852:Epoxy Compounds; C013658:propylene; D007501:Iron
Density functional theory; Epoxidation; Hydroxylation; Non-heme; Steric hindrance