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Visible-Light-Induced Olefin Activation Using 3D Aromatic Boron-Rich Cluster Photooxidants

Messina, Marco S. and Axtell, Jonathan C. and Wang, Yiqun and Chong, Paul and Wixtrom, Alex I. and Kirlikovali, Kent O. and Upton, Brianna M. and Hunter, Bryan M. and Shafaat, Oliver S. and Khan, Saeed I. and Winkler, Jay R. and Gray, Harry B. and Alexandrova, Anastassia N. and Maynard, Heather D. and Spokoyny, Alexander M. (2016) Visible-Light-Induced Olefin Activation Using 3D Aromatic Boron-Rich Cluster Photooxidants. Journal of the American Chemical Society, 138 (22). pp. 6952-6955. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20160613-124225978

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Abstract

We report a discovery that perfunctionalized icosahedral dodecaborate clusters of the type B_(12)(OCH_2Ar)_(12) (Ar = Ph or C_6F_5) can undergo photo-excitation with visible light, leading to a new class of metal-free photooxidants. Excitation in these species occurs as a result of the charge transfer between low-lying orbitals located on the benzyl substituents and an unoccupied orbital delocalized throughout the boron cluster core. Here we show how these species, photo-excited with a benchtop blue LED source, can exhibit excited-state reduction potentials as high as 3 V and can participate in electron-transfer processes with a broad range of styrene monomers, initiating their polymerization. Initiation is observed in cases of both electron-rich and electron-deficient styrene monomers at cluster loadings as low as 0.005 mol%. Furthermore, photo-excitation of B_(12)(OCH_2C_6F_5)_(12) in the presence of a less activated olefin such as isobutylene results in the production of highly branched poly(isobutylene). This work introduces a new class of air-stable, metal-free photo-redox reagents capable of mediating chemical transformations.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jacs.6b03568DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jacs.6b03568PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jacs.6b03568PublisherSupporting Information
http://escholarship.org/uc/item/7zz1g6fxOrganizationUniversity of California eScholarship
ORCID:
AuthorORCID
Messina, Marco S.0000-0003-2827-118X
Axtell, Jonathan C.0000-0002-5579-4296
Wixtrom, Alex I.0000-0002-0622-4633
Hunter, Bryan M.0000-0001-8559-9304
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
Alexandrova, Anastassia N.0000-0002-3003-1911
Spokoyny, Alexander M.0000-0002-5683-6240
Additional Information:© 2016 American Chemical Society. Received: April 6, 2016. Published: May 17, 2016. A.M.S. thanks the UCLA Department of Chemistry and Biochemistry for start-up funds and 3M for a Non-Tenured Faculty Award. M.S.M. thanks the NSF for the Bridge-to-Doctorate and the Predoctoral (GRFP) Fellowships. H.B.G. and O.S.S. acknowledge funding from the NIH (R01DK019038) and the Arnold and Mabel Beckman Foundation. A.N.A. thanks the NSF for CAREER Award CHE-1351968. Y.W. thanks the CSST Scholarship. H.D.M. thanks the NSF (CHE-1507735) for funding. B.M.U. thanks UCLA for a Dissertation Year Fellowship. The authors thank Mr. Daniel Hatfield (UCLA) for assistance with computational studies and Prof. Andrea Kasko (UCLA) for generously allowing access to her GPC instrument. Author Contributions: M.S.M. and J.C.A. contributed equally to the project. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
UCLAUNSPECIFIED
3MUNSPECIFIED
NSF Predoctoral FellowshipUNSPECIFIED
NIHR01DK019038
Arnold and Mabel Beckman FoundationUNSPECIFIED
NSFCHE-1351968
NSFCHE-1507735
Issue or Number:22
Record Number:CaltechAUTHORS:20160613-124225978
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160613-124225978
Official Citation:Visible-Light-Induced Olefin Activation Using 3D Aromatic Boron-Rich Cluster Photooxidants Marco S. Messina, Jonathan C. Axtell, Yiqun Wang, Paul Chong, Alex I. Wixtrom, Kent O. Kirlikovali, Brianna M. Upton, Bryan M. Hunter, Oliver S. Shafaat, Saeed I. Khan, Jay R. Winkler, Harry B. Gray, Anastassia N. Alexandrova, Heather D. Maynard, and Alexander M. Spokoyny Journal of the American Chemical Society 2016 138 (22), 6952-6955 DOI: 10.1021/jacs.6b03568
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:67877
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:13 Jun 2016 20:57
Last Modified:09 Mar 2020 13:19

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