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Explorations of the nonheme high-valent iron-oxo landscape: crystal structure of a synthetic complex with an [FeIV2(μ-O)2] diamond core relevant to the chemistry of sMMOH

Journal Article · · Faraday Discussions
DOI:https://doi.org/10.1039/d1fd00066g· OSTI ID:1982204
 [1];  [1];  [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States)
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Methanotrophic bacteria utilize methane monooxygenase (MMO) to carry out the first step in metabolizing methane. The soluble enzymes employ a hydroxylase component (sMMOH) with a nonheme diiron active site that activates O2 and generates a powerful oxidant capable of converting methane to methanol. It is proposed that the diiron(II) center in the reduced enzyme reacts with O2 to generate a diferric-peroxo intermediate called P that then undergoes O–O cleavage to convert into a diiron(IV) derivative called Q, which carries out methane hydroxylation. Most (but not all) of the spectroscopic data of Q accumulated by various groups to date favor the presence of an FeIV2(μ-O)2 unit with a diamond core. The Que lab has had a long-term interest in making synthetic analogs of iron enzyme intermediates. To this end, the first crystal structure of a complex with a FeIIIFeIV(μ-O)2 diamond core was reported in 1999, which exhibited an Fe∙∙∙Fe distance of 2.683(1) Å. Now more than 20 years later, a complex with an FeIV2(μ-O)2 diamond core has been synthesized in sufficient purity to allow diffraction-quality crystals to be grown. Finally, its crystal structure has been solved, revealing an Fe∙∙∙Fe distance of 2.711(4) Å for comparison with structural data for related complexes with lower iron oxidation states.
Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Sponsoring Organization:
National Institutes of Health (NIH); USDOE; USDOE Office of Science (SC)
Grant/Contract Number:
AC02-98CH10886; SC0012704
OSTI ID:
1982204
Alternate ID(s):
OSTI ID: 1845598
Journal Information:
Faraday Discussions, Journal Name: Faraday Discussions Vol. 234; ISSN 1359-6640
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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