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Effects of Lewis Acidic Metal Ions (M) on Oxygen-Atom Transfer Reactivity of Heterometallic Mn_3MO_4 Cubane and Fe_3MO(OH) and Mn_3MO(OH) Clusters

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 Mn_3MO_4 Cubane and Fe_3MO(OH) and Mn_3MO(OH) Clusters. Inorganic Chemistry, 58 (4). pp. 2336-2345. ISSN 0020-1669. PMCID PMC6574207. http://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 Mn_3 and Fe_3 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 [Mn_3MO_4], [Mn_3MO(OH)], and [Fe_3MO(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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.inorgchem.8b02701DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/acs.inorgchem.8b02701PublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6574207PubMed CentralArticle
ORCID:
AuthorORCID
Lionetti, Davide0000-0002-4937-886X
Tsui, Emily Y.0000-0001-6419-3954
Stich, Troy A.0000-0003-0710-1456
Carsch, Kurtis M.0000-0003-4432-7518
Nielsen, Robert J.0000-0002-7962-0186
Goddard, William A., III0000-0003-0097-5716
Britt, R. David0000-0003-0889-8436
Agapie, Theodor0000-0002-9692-7614
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
Funders:
Funding AgencyGrant Number
CaltechUNSPECIFIED
NIHR01 GM102687A
Camille and Henry Dreyfus FoundationUNSPECIFIED
Resnick Sustainability InstituteUNSPECIFIED
NSFCBET-1512759
NSFCHE-0639094
NSFACI-1548562
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1324
PubMed Central ID:PMC6574207
Record Number:CaltechAUTHORS:20190207-142044105
Persistent URL:http://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:19 Jun 2019 18:08

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