0472718 - ÚFCH JH 2017 RIV GB eng M - Část monografie knihy
Solomon, E. I. - Sutherlin, K. D. - Srnec, Martin
High-Spin and Low-Spin States in {FeNO}(7), Fe-IV=O, and Fe-III-OOH Complexes and Their Correlations to Reactivity.
Spin States in Biochemistry and Inorganic Chemistry: Influence on Structure and Reactivity. 1. Chichester: JOHN WILEY & SONS LTD, 2016 - (Swart, M.; Costas, M.), s. 369-407. ISBN 978-1-118-89830-7
Institucionální podpora: RVO:61388955
Klíčová slova: RESONANCE VIBRATIONAL SPECTROSCOPY * O-O BOND * NONHEME OXOIRON(IV) COMPLEXES
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie

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).
Trvalý link: http://hdl.handle.net/11104/0269947