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

The result's identifiers

  • Result code in IS VaVaI

    <a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F16%3A00472718" target="_blank" >RIV/61388955:_____/16:00472718 - isvavai.cz</a>

  • Result on the web

  • DOI - Digital Object Identifier

Alternative languages

  • Result language

    angličtina

  • Original language name

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

  • Original language description

    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).

  • Czech name

  • Czech description

Classification

  • Type

    C - Chapter in a specialist book

  • CEP classification

    CF - Physical chemistry and theoretical chemistry

  • OECD FORD branch

Result continuities

  • Project

  • Continuities

    I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Others

  • Publication year

    2016

  • Confidentiality

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

Data specific for result type

  • Book/collection name

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

  • ISBN

    978-1-118-89830-7

  • Number of pages of the result

    39

  • Pages from-to

    369-407

  • Number of pages of the book

    448

  • Publisher name

    JOHN WILEY & SONS LTD

  • Place of publication

    Chichester

  • UT code for WoS chapter