High-Spin and Low-Spin States in {FeNO}(7), Fe-IV=O, and Fe-III-OOH Complexes and Their Correlations to Reactivity

Kód výsledku v IS VaVaI

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Výsledek na webu

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DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

High-Spin and Low-Spin States in {FeNO}(7), Fe-IV=O, and Fe-III-OOH Complexes and Their Correlations to Reactivity

Popis výsledku v původním jazyce

This chapter presents a detailed discussion of high-spin and low-spin states in (FeNO)7 (S = 3/2, 1/2), FeIV=O (S = 2, 1), and FeIIIOOH (S = 5/2, 1/2) complexes, their frontier molecular orbitals (FMOs, that is, low-lying unoccupied molecular orbitals (MOs) with proper orbital character and orientation for attack on substrate), and their contributions to reactivity in model and enzyme systems. Five-coordinate ferrous sites in nonheme Fe enzymes generally have low reactivity with O2 unless both substrate and cofactor necessary for the reaction are present. Analysis of the magnetic circular dichroism (MCD) spectra of the models has elucidated the FMOs available for reactivity in each spin state, and nuclear resonance vibrational spectroscopy (NRVS) coupled to density functional theory (DFT) calculations has defined the geometric contributions to H-atom abstraction (HAA) and oxygen-atom transfer (OAT) reactivity in the models and the HAA reactivity of the FeIV=O enzyme intermediate in syringomicyn halogenase (SyrB2).

Název v anglickém jazyce

High-Spin and Low-Spin States in {FeNO}(7), Fe-IV=O, and Fe-III-OOH Complexes and Their Correlations to Reactivity

Popis výsledku anglicky

This chapter presents a detailed discussion of high-spin and low-spin states in (FeNO)7 (S = 3/2, 1/2), FeIV=O (S = 2, 1), and FeIIIOOH (S = 5/2, 1/2) complexes, their frontier molecular orbitals (FMOs, that is, low-lying unoccupied molecular orbitals (MOs) with proper orbital character and orientation for attack on substrate), and their contributions to reactivity in model and enzyme systems. Five-coordinate ferrous sites in nonheme Fe enzymes generally have low reactivity with O2 unless both substrate and cofactor necessary for the reaction are present. Analysis of the magnetic circular dichroism (MCD) spectra of the models has elucidated the FMOs available for reactivity in each spin state, and nuclear resonance vibrational spectroscopy (NRVS) coupled to density functional theory (DFT) calculations has defined the geometric contributions to H-atom abstraction (HAA) and oxygen-atom transfer (OAT) reactivity in the models and the HAA reactivity of the FeIV=O enzyme intermediate in syringomicyn halogenase (SyrB2).

Druh

C - Kapitola v odborné knize

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

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Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2016

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název knihy nebo sborníku

Spin States in Biochemistry and Inorganic Chemistry: Influence on Structure and Reactivity

ISBN

978-1-118-89830-7

Počet stran výsledku

39

Strana od-do

369-407

Počet stran knihy

448

Název nakladatele

JOHN WILEY & SONS LTD

Místo vydání

Chichester

Kód UT WoS kapitoly

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