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Iron and manganese oxo complexes, oxo wall and beyond

Title
Iron and manganese oxo complexes, oxo wall and beyond
Authors
Larson, Virginia A.Battistella, BeatriceRay, KallolLehnert, NicolaiNam, Wonwoo
Ewha Authors
남원우
SCOPUS Author ID
남원우scopus
Issue Date
2020
Journal Title
NATURE REVIEWS CHEMISTRY
ISSN
2397-3358JCR Link
Citation
NATURE REVIEWS CHEMISTRY vol. 4, no. 8, pp. 404 - 419
Publisher
NATURE PUBLISHING GROUP
Indexed
SCIE; SCOPUS WOS scopus
Document Type
Review
Abstract
High-valent metal-oxo species with multiply-bonded M-O groups have been proposed as key intermediates in many biological and abiological catalytic oxidation reactions. These intermediates are implicated as active oxidants in alkane hydroxylation, olefin epoxidation and other oxidation reactions. For example, [(FeO)-O-iv(porphyrinato(center dot-))](+)cofactors bearing pi-radical porphyrinato(center dot-)ligands oxidize organic substrates in cytochrome P450 enzymes, which are common to many life forms. Likewise, high-valent Mn-oxo species are active for H2O oxidation in photosystem II. The chemistry of these native reactive species has inspired chemists to prepare highly oxidized transition-metal complexes as functional mimics. Although many synthetic Fe-O and Mn-O complexes now exist, the analogous oxo complexes of the late transition metals (groups 9-11) are rare. Indeed, late-transition-metal-oxo complexes of tetragonal (fourfold) symmetry should be electronically unstable, a rule commonly referred to as the 'oxo wall'. A few late metal-oxos have been prepared by targeting other symmetries or unusual spin states. These complexes have been studied using spectroscopic and theoretical methods. This Review describes mononuclear non-haem Fe-O and Mn-O species, the nature of the oxo wall and recent advances in the preparation of oxo complexes of Co, Ni and Cu beyond the oxo wall.
DOI
10.1038/s41570-020-0197-9
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자연과학대학 > 화학·나노과학전공 > Journal papers
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