Lionetti, Davide and Suseno, Sandy and Tsui, Emily Y. and Lu, Luo and Stich, Troy A. and Carsch, Kurtis M. and Nielsen, Robert J. and Goddard, William A., III and Britt, R. David and Agapie, Theodor (2019) Effects of Lewis Acidic Metal Ions (M) on Oxygen-Atom Transfer Reactivity of Heterometallic Mn₃MO₄ Cubane and Fe₃MO(OH) and Mn₃MO(OH) Clusters. Inorganic Chemistry, 58 (4). pp. 2336-2345. ISSN 0020-1669. PMCID PMC6574207. doi:10.1021/acs.inorgchem.8b02701. https://resolver.caltech.edu/CaltechAUTHORS:20190207-142044105
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Abstract
The modulation of the reactivity of metal oxo species by redox inactive metals has attracted much interest due to the observation of redox inactive metal effects on processes involving electron transfer both in nature (the oxygen-evolving complex of Photosystem II) and in heterogeneous catalysis (mixed-metal oxides). Studies of small-molecule models of these systems have revealed numerous instances of effects of redox inactive metals on electron- and group-transfer reactivity. However, the heterometallic species directly involved in these transformations have rarely been structurally characterized and are often generated in situ. We have previously reported the preparation and structural characterization of multiple series of heterometallic clusters based on Mn₃ and Fe₃ cores and described the effects of Lewis acidity of the heterometal incorporated in these complexes on cluster reduction potential. To determine the effects of Lewis acidity of redox inactive metals on group transfer reactivity in structurally well-defined complexes, we studied [Mn₃MO_₄, [Mn₃MO(OH)], and [Fe₃MO(OH)] clusters in oxygen atom transfer (OAT) reactions with phosphine substrates. The qualitative rate of OAT correlates with the Lewis acidity of the redox inactive metal, confirming that Lewis acidic metal centers can affect the chemical reactivity of metal oxo species by modulating cluster electronics.
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| Alternate Title: | Effects of Lewis Acidic Metal Ions (M) on Oxygen-Atom Transfer Reactivity of Heterometallic Mn3MO4 Cubane and Fe3MO(OH) and Mn3MO(OH) Clusters | ||||||||||||||||||
| Additional Information: | © 2019 American Chemical Society. Received: September 21, 2018. Publication Date (Web): February 7, 2019. Accession Codes: CCDC 1035166 and 1035222 contain the supplementary crystallographic data for this paper. This work was supported by the California Institute of Technology and the NIH R01 GM102687A (T.A.). T.A. is a Dreyfus fellow. We thank Dr. Michael K. Takase and Lawrence M. Henling for assistance with X-ray crystallography. D.L. gratefully acknowledges a graduate fellowship from the Resnick Sustainability Institute at Caltech. K.C. and W.A.G. received support from the NSF (CBET-1512759). The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF Chemistry Research Instrumentation award to Caltech (CHE-0639094). Computational resources included the Extreme Science and Engineering Discovery Environment, which is supported by National Science Foundation Grant ACI-1548562. The authors declare no competing financial interest. | ||||||||||||||||||
| Group: | Resnick Sustainability Institute | ||||||||||||||||||
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| Issue or Number: | 4 | ||||||||||||||||||
| PubMed Central ID: | PMC6574207 | ||||||||||||||||||
| DOI: | 10.1021/acs.inorgchem.8b02701 | ||||||||||||||||||
| Record Number: | CaltechAUTHORS:20190207-142044105 | ||||||||||||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20190207-142044105 | ||||||||||||||||||
| Official Citation: | Effects of Lewis Acidic Metal Ions (M) on Oxygen-Atom Transfer Reactivity of Heterometallic Mn3MO4 Cubane and Fe3MO(OH) and Mn3MO(OH) Clusters. Davide Lionetti, Sandy Suseno, Emily Y. Tsui, Luo Lu, Troy A. Stich, Kurtis M. Carsch, Robert J. Nielsen, William A. Goddard, III, R. David Britt, and Theodor Agapie. Inorganic Chemistry 2019 58 (4), 2336-2345. DOI: 10.1021/acs.inorgchem.8b02701 | ||||||||||||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||||||||||||
| ID Code: | 92766 | ||||||||||||||||||
| Collection: | CaltechAUTHORS | ||||||||||||||||||
| Deposited By: | Tony Diaz | ||||||||||||||||||
| Deposited On: | 08 Feb 2019 00:21 | ||||||||||||||||||
| Last Modified: | 01 Mar 2022 18:30 |
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