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Title: Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3Mn-Iodosobenzene Adducts

Abstract

In this paper, we report the synthesis, characterization, and reactivity of [LFe3(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, 57Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (FeIII2FeIIMnII vs. FeIII3MnII) influence oxygen atom transfer in tetranuclear Fe3Mn clusters. Finally, 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.

Authors:
 [1];  [1];  [2];  [2];  [1];  [1];  [2]; ORCiD logo [1]
  1. California Inst. of Technology (CalTech), Pasadena, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Inst. of Health (NIH) (United States)
OSTI Identifier:
1379810
Alternate Identifier(s):
OSTI ID: 1401528
Grant/Contract Number:  
AC02-05CH11231; R01-GM102687B; DEAC02- 05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 17; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; C-H bond oxygenation; clusters; iodosobenzene adduct; multimetallic complexes; oxygen atom transfer

Citation Formats

de Ruiter, Graham, Carsch, Kurtis M., Gul, Sheraz, Chatterjee, Ruchira, Thompson, Niklas B., Takase, Michael K., Yano, Junko, and Agapie, Theodor. Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3Mn-Iodosobenzene Adducts. United States: N. p., 2017. Web. doi:10.1002/anie.201701319.
de Ruiter, Graham, Carsch, Kurtis M., Gul, Sheraz, Chatterjee, Ruchira, Thompson, Niklas B., Takase, Michael K., Yano, Junko, & Agapie, Theodor. Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3Mn-Iodosobenzene Adducts. United States. https://doi.org/10.1002/anie.201701319
de Ruiter, Graham, Carsch, Kurtis M., Gul, Sheraz, Chatterjee, Ruchira, Thompson, Niklas B., Takase, Michael K., Yano, Junko, and Agapie, Theodor. Fri . "Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3Mn-Iodosobenzene Adducts". United States. https://doi.org/10.1002/anie.201701319. https://www.osti.gov/servlets/purl/1379810.
@article{osti_1379810,
title = {Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3Mn-Iodosobenzene Adducts},
author = {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},
abstractNote = {In this paper, we report the synthesis, characterization, and reactivity of [LFe3(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, 57Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (FeIII2FeIIMnII vs. FeIII3MnII) influence oxygen atom transfer in tetranuclear Fe3Mn clusters. Finally, 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.},
doi = {10.1002/anie.201701319},
journal = {Angewandte Chemie (International Edition)},
number = 17,
volume = 56,
place = {United States},
year = {2017},
month = {3}
}

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Figures / Tables:

Figure 1 Figure 1: General molecular structure of [LFe3(PhPz)3OMn]n+ 3 (n = 2–3; top left), supported by pyrazolates and a 1,3,5- triarylbenzene-based ligand. The inset shows the coloring scheme for the metal oxidation states.

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.