caa a22 4500 605507120 CHVBK 20210128100630.0 cr unu---uuuuu 210128e20151001xx s 000 0 eng 10.1007/s00775-015-1294-y doi (NATIONALLICENCE)springer-10.1007/s00775-015-1294-y What factors influence the reactivity of C-H hydroxylation and C=C epoxidation by [FeIV(Lax)(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)(O)]n+ [Elektronische Daten] [Wang Yi, Liu Yuan, Yang Kun, He Zhengwen, Tian Jing, Fei xu, Guo Hong, Wang Yong] Density functional theory is used to investigate geometric structures and mechanisms for hydroxylation and epoxidation from propene for four non-heme iron complexes, [FeIV(Lax)(TMC)(O)]n+, which are the inverted isomers of [FeIV(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 [FeIV(Lax)(TMC)(O)]n+ than that in [FeIV(O)(TMC)(Lax)]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 [FeIV(Lax)(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 (Lax=TF, N3, SR) complexes chemoselectively hydroxylate even in the presence of a C=C double bond. SBIC, 2015 Non-heme nationallicence Steric hindrance nationallicence Hydroxylation nationallicence Epoxidation nationallicence Density functional theory nationallicence Yi Wang School of Biological Engineering, Dalian Polytechnic University, 116034, Dalian, China aut Yuan Liu School of Biological Engineering, Dalian Polytechnic University, 116034, Dalian, China aut Kun Yang Department of Physics, Dalian Maritime University, 1 Linghai Road, 116026, Dalian, China aut Zhengwen He School of Biological Engineering, Dalian Polytechnic University, 116034, Dalian, China aut Jing Tian School of Biological Engineering, Dalian Polytechnic University, 116034, Dalian, China aut xu Fei School of Biological Engineering, Dalian Polytechnic University, 116034, Dalian, China aut Hong Guo School of Biological Engineering, Dalian Polytechnic University, 116034, Dalian, China aut Yong Wang State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, 730000, Lanzhou, China aut JBIC Journal of Biological Inorganic Chemistry Springer Berlin Heidelberg 20/7(2015-10-01), 1123-1134 0949-8257 20:7<1123 2015 20 775 https://doi.org/10.1007/s00775-015-1294-y text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00775-015-1294-y text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Yi Wang School of Biological Engineering, Dalian Polytechnic University, 116034, Dalian, China aut NATIONALLICENCE 700 1- Yuan Liu School of Biological Engineering, Dalian Polytechnic University, 116034, Dalian, China aut NATIONALLICENCE 700 1- Kun Yang Department of Physics, Dalian Maritime University, 1 Linghai Road, 116026, Dalian, China aut NATIONALLICENCE 700 1- Zhengwen He School of Biological Engineering, Dalian Polytechnic University, 116034, Dalian, China aut NATIONALLICENCE 700 1- Jing Tian School of Biological Engineering, Dalian Polytechnic University, 116034, Dalian, China aut NATIONALLICENCE 700 1- xu Fei School of Biological Engineering, Dalian Polytechnic University, 116034, Dalian, China aut NATIONALLICENCE 700 1- Hong Guo School of Biological Engineering, Dalian Polytechnic University, 116034, Dalian, China aut NATIONALLICENCE 700 1- Yong Wang State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, 730000, Lanzhou, China aut NATIONALLICENCE 773 0- JBIC Journal of Biological Inorganic Chemistry Springer Berlin Heidelberg 20/7(2015-10-01), 1123-1134 0949-8257 20:7<1123 2015 20 775