Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3Mn-Iodosobenzene Adducts
Abstract
Abstract We report the synthesis, characterization, and reactivity of [LFe 3 (PhPz) 3 OMn( s PhIO)][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 2 Fe II Mn II vs. Fe III 3 Mn II ) influence oxygen atom transfer in tetranuclear Fe 3 Mn 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.
- Authors:
-
- California Inst. of Technology (CalTech), Pasadena, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (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 = {Abstract We report the synthesis, characterization, and reactivity of [LFe 3 (PhPz) 3 OMn( s PhIO)][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 2 Fe II Mn II vs. Fe III 3 Mn II ) influence oxygen atom transfer in tetranuclear Fe 3 Mn 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.},
doi = {10.1002/anie.201701319},
journal = {Angewandte Chemie (International Edition)},
number = 17,
volume = 56,
place = {United States},
year = {Fri Mar 24 00:00:00 EDT 2017},
month = {Fri Mar 24 00:00:00 EDT 2017}
}
Web of Science
Figures / Tables:
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