101. Synthesis, reactivity, and DFT studies of a series of non-heme alkoxoiron(III) complexes as models for lipoxygenase.
- Author
-
Wu, Guiling, Ci, Chenggang, and Li, Dongfeng
- Subjects
- *
CHEMICAL bond lengths , *RED , *LIPOXYGENASES - Abstract
Four alkoxoiron(III) complexes of N,N,N′,N′-tetrakis(2-benzimidazolyl-methyl)- ortho -diamine- trans -cyclohexane (ctb) in alcohol/MeCN have been synthesized and characterized as models of lipoxygenase. [Display omitted] • Four novel lipoxygenase model complexes were synthesized and characterized. • These alkoxoiron(III) complexes could be reduced with alkene via H-abstraction reaction. • The total reaction rate might be mainly contributed by the subsequent H-abstractions. Four lipoxygenase model complexes, [FeIII(OMe)(Hctb)](ClO 4) 3 ·3MeOH·4.5H 2 O (1), [FeIII(OEt)(Hctb)](ClO 4) 3 ·EtOH (2), [FeIII(OPr n)(Hctb)](ClO 4) 3 · n -PrOH·H 2 O (3) and [FeIII(OBu n)(Hctb)](ClO 4) 3 · n -BuOH·H 2 O (4) have been synthesized by reacting N,N,N′,N′-tetrakis(2-benzimidazolyl-methyl)- ortho -diamine- trans -cyclohexane (ctb) with Fe(ClO 4) 3 ·9H 2 O in alcohol/MeCN. These alkoxoiron(III) complexes all possess (i) an octahedral Fe(III)-OR center (R = Me, 1 ; Et, 2 ; n -Pr, 3 ; n -Bu, 4) with Fe-O bond lengths between 1.79 and 1.81 Å, (ii) a red-yellow colour, and (iii) an intense electronic transition around 370 nm. Complexes 1 – 4 can be reduced by cis , cis -1,4-diene via a H-abstraction mechanism. DFT calculations reveal the reaction rates are attributed to the H-abstraction reaction between the alkoxy unit and conjugated alkene. [ABSTRACT FROM AUTHOR]
- Published
- 2021
- Full Text
- View/download PDF