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Accelerated Oxygen Atom Transfer and C−H Bond Oxygenation by Remote Redox Changes in Fe_3Mn-Iodosobenzene Adducts

De Ruiter, Graham and Carsch, Kurtis M. and Gul, Sheraz and Chatterjee, Ruchira and Thompson, Niklas B. and Takase, Michael K. and Yano, Junko and Agapie, Theodor (2017) Accelerated Oxygen Atom Transfer and C−H Bond Oxygenation by Remote Redox Changes in Fe_3Mn-Iodosobenzene Adducts. Angewandte Chemie International Edition, 56 (17). pp. 4772-4776. ISSN 1433-7851. PMCID PMC5505263. doi:10.1002/anie.201701319.

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We report the synthesis, characterization, and reactivity of [Lfe_3(PhPz)_3OMn(^sPhIO)][OTf]_x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene–metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, ^(57)Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe^(III)_2Fe^(II)Mn^(II) vs. Fe^(III)_3Mn^(II)) influence oxygen atom transfer in tetranuclear Fe_3Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.

Item Type:Article
Related URLs:
URLURL TypeDescription CentralArticle
Carsch, Kurtis M.0000-0003-4432-7518
Gul, Sheraz0000-0001-8920-8737
Chatterjee, Ruchira0000-0002-0865-061X
Thompson, Niklas B.0000-0003-2745-4945
Takase, Michael K.0000-0001-8365-3645
Yano, Junko0000-0001-6308-9071
Agapie, Theodor0000-0002-9692-7614
Alternate Title:Accelerated Oxygen Atom Transfer and C–H Bond Oxygenation by Remote Redox Changes in Fe3Mn-Iodosobenzene Adducts
Additional Information:© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Version of record online: 24 March 2017; Manuscript Received: 6 February 2017. This research was supported by the NIH (R01-GM102687B). T.A. is grateful for Dreyfus and Cottrell fellowships. K.M.C is grateful for a Summer Undergraduate Research Fellowship. We thank Lawrence M. Henling for assistance with X-ray crystallography. Part of this research (XAS data collection) was carried out on beamline 7-3 at the SSRL, operated by Stanford University for the US DOE Office of Science, and supported by the DOE and NIH. XAS studies were performed with support of the Office of Science, OBES, Division of Chemical Sciences, Geosciences, and Biosciences (CSGB) of the DOE under contract no. DE-AC02-05CH11231 (J.Y.).
Funding AgencyGrant Number
Camille and Henry Dreyfus FoundationUNSPECIFIED
Cottrell Scholar of Research CorporationUNSPECIFIED
Caltech Summer Undergraduate Research Fellowship (SURF)UNSPECIFIED
Department of Energy (DOE)DEAC02-05CH11231
Subject Keywords:C−H bond oxygenation; clusters; iodosobenzene adduct; multimetallic complexes; oxygen atom transfer
Issue or Number:17
PubMed Central ID:PMC5505263
Record Number:CaltechAUTHORS:20170324-141105678
Persistent URL:
Official Citation:G. de Ruiter, K. M. Carsch, S. Gul, R. Chatterjee, N. B. Thompson, M. K. Takase, J. Yano, T. Agapie, Angew. Chem. Int. Ed. 2017, 56, 4772
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:75394
Deposited By: Tony Diaz
Deposited On:24 Mar 2017 22:14
Last Modified:28 Mar 2022 22:45

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