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A Highly Reactive Oxoiron(IV) Complex Supported by a Bioinspired N3 O Macrocyclic Ligand.

ABSTRACT: The sluggish oxidants [FeIV (O)(TMC)(CH3 CN)]2+ (TMC=1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and [FeIV (O)(TMCN-d12 )(OTf)]+ (TMCN-d12 =1,4,7,11-tetra(methyl-d3 )-1,4,7,11-tetraazacyclotetradecane) are transformed into the highly reactive oxidant [FeIV (O)(TMCO)(OTf)]+ (1; TMCO=4,8,12-trimethyl-1-oxa-4,8,12-triazacyclotetradecane) upon replacement of an NMe donor in the TMC and TMCN ligands by an O?atom. A rate enhancement of five to six orders of magnitude in both H?atom and O?atom transfer reactions was observed upon oxygen incorporation into the macrocyclic ligand. This finding was explained in terms of the higher electrophilicity of the iron center and the higher availability of the more reactive S=2 state in 1. This rationalizes nature's preference for using O-rich ligand environments for the hydroxylation of strong C-H bonds in enzymatic reactions.

SUBMITTER: Monte Perez I

PROVIDER: S-EPMC5679783 | biostudies-literature | 2017 Nov

REPOSITORIES: biostudies-literature

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A Highly Reactive Oxoiron(IV) Complex Supported by a Bioinspired N3 O Macrocyclic Ligand.

Monte Pérez Inés I Engelmann Xenia X Lee Yong-Min YM Yoo Mi M Kumaran Elumalai E Farquhar Erik R ER Bill Eckhard E England Jason J Nam Wonwoo W Swart Marcel M Ray Kallol K

Angewandte Chemie (International ed. in English) 20171017 46

The sluggish oxidants [FeIV (O)(TMC)(CH3 CN)]2+ (TMC=1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and [FeIV (O)(TMCN-d12 )(OTf)]+ (TMCN-d12 =1,4,7,11-tetra(methyl-d3 )-1,4,7,11-tetraazacyclotetradecane) are transformed into the highly reactive oxidant [FeIV (O)(TMCO)(OTf)]+ (1; TMCO=4,8,12-trimethyl-1-oxa-4,8,12-triazacyclotetradecane) upon replacement of an NMe donor in the T ...[more]

PMID: 28945949

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Project description:The pentadentate ligand (n)Bu-P2DA (2(b), (n)Bu-P2DA = N-(1',1'-bis(2-pyridyl)pentyl)iminodiacetate) was designed to bind an iron center in a carboxylate-rich environment similar to that found in the active sites of TauD and other α-ketoglutarate-dependent mononuclear non-heme iron enzymes. The iron(II) complex (n)Bu(4)N[Fe(II)(Cl)((n)Bu-P2DA)] (3(b)-Cl) was synthesized and crystallographically characterized to have a 2-pyridine-2-carboxylate donor set in the plane perpendicular to the Fe-Cl bond. Reaction of 3(b)-Cl with N-heterocyclic amines such as pyridine or imidazole yielded the N-heterocyclic amine adducts [Fe(II)(N)((n)Bu-P2DA)]. These adducts in turn reacted with oxo-transfer reagents at -95 °C to afford a short-lived oxoiron(IV) complex [Fe(IV)(O)((n)Bu-P2DA)] (5(b)) in yields as high as 90% depending on the heterocycle used. Complex 5(b) exhibits near-IR absorption features (λ(max) = 770 nm) and Mossbauer parameters (δ = 0.04 mm/s; ΔE(Q) = 1.13 mm/s; D = 27±2 cm(-1)) characteristic of an S = 1 oxoiron(IV) species. Direct evidence for an Fe=O bond of 1.66 Å was found from EXAFS analysis. DFT calculations on 5(b) in its S =1 spin state afforded a geometry-optimized structure consistent with the EXAFS data. They further demonstrated that the replacement of two pyridine donors in [Fe(IV)(O)(N4Py)](2+) (N4Py = N,N-(bis(2-pyridyl)methyl)N-bis(2-pyridylmethyl)amine) with carboxylate donors in 5(b) decreased the energy gap between the ground S = 1 and the excited S = 2 states, reflecting the weaker equatorial ligand field of 5(b) and accounting for its larger D value. Complex 5(b) reacted readily with dihydrotoluene, methyldiphenylphosphine and ferrocene at -60 °C, and in all cases was approximately a 5-fold more reactive oxidant than [Fe(IV)(O)(N4Py)](2+). The reactivity differences between these two complexes may arise from a combination of electronic and steric factors. Carboxylate-rich 5(b) represents the closest structural mimic reported thus far of the oxoiron(IV) intermediate ('J') found in TauD and provides us with vital insights into the role carboxylate ligands play in modulating the spectroscopic and reactivity properties of the non-heme oxoiron(IV) moiety.

Dataset Information

A Highly Reactive Oxoiron(IV) Complex Supported by a Bioinspired N3 O Macrocyclic Ligand.

Publications

A Highly Reactive Oxoiron(IV) Complex Supported by a Bioinspired N<sub>3</sub> O Macrocyclic Ligand.

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