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Seeing the cis-Dihydroxylating Intermediate: A Mononuclear Nonheme Iron-Peroxo Complex in cis-Dihydroxylation Reactions Modeling Rieske Dioxygenases

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.2c13551· OSTI ID:1991528
 [1];  [2];  [3];  [4];  [5];  [2];  [2];  [4];  [3];  [6]
  1. Ewha Womans Univ., Seoul (Korea, Republic of); slac
  2. Ewha Womans Univ., Seoul (Korea, Republic of)
  3. Carnegie Mellon Univ., Pittsburgh, PA (United States)
  4. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  5. Ewha Womans Univ., Seoul (Korea, Republic of); Shandong Univ., Qingdao, Shandong (China)
  6. Ewha Womans Univ., Seoul (Korea, Republic of); Univ. of Jinan (China)
+ Show Author Affiliations
The nature of reactive intermediates and the mechanism of the cis-dihydroxylation of arenes and olefins by Rieske dioxygenases and synthetic nonheme iron catalysts have been the topic of intense research over the past several decades. In this study, we report that a spectroscopically well characterized mononuclear nonheme iron(III)-peroxo complex reacts with olefins and naphthalene derivatives, yielding iron(III) cycloadducts that are isolated and characterized structurally and spectroscopically. Further, kinetics and product analysis reveal that the nonheme iron(III)-peroxo complex is a nucleophile that reacts with olefins and naphthalenes to yield cis-diol products. The present study reports the first example of the cis-dihydroxylation of substrates by a nonheme iron(III)-peroxo complex that yields cis-diol products.
Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
National Institute of General Medical Sciences (NIGMS); National Institute of Health (NIH); National Research Foundation (NRF) of Korea; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1991528
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 8 Vol. 145; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
aromatic compounds
chemical reactions
hydrocarbons
iron
styrenes