Effects of Lewis Acidic Metal Ions (M) on Oxygen-Atom Transfer Reactivity of Heterometallic Mn₃MO₄ Cubane and Fe₃MO(OH) and Mn₃MO(OH) Clusters
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.
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.Attached Files
Accepted Version - nihms-1023538.pdf
Supplemental Material - ic8b02701_si_001.pdf
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Additional details
- Alternative title
- Effects of Lewis Acidic Metal Ions (M) on Oxygen-Atom Transfer Reactivity of Heterometallic Mn3MO4 Cubane and Fe3MO(OH) and Mn3MO(OH) Clusters
- PMCID
- PMC6574207
- Eprint ID
- 92766
- DOI
- 10.1021/acs.inorgchem.8b02701
- Resolver ID
- CaltechAUTHORS:20190207-142044105
- Caltech
- NIH
- R01 GM102687A
- Camille and Henry Dreyfus Foundation
- Resnick Sustainability Institute
- NSF
- CBET-1512759
- NSF
- CHE-0639094
- NSF
- ACI-1548562
- Created
-
2019-02-08Created from EPrint's datestamp field
- Updated
-
2022-03-01Created from EPrint's last_modified field
- Caltech groups
- Resnick Sustainability Institute
- Other Numbering System Name
- WAG
- Other Numbering System Identifier
- 1324