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Metal-free photochemical silylations and transfer hydrogenations of benzenoid hydrocarbons and graphene
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics. Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Applied Materials Sciences. (Electron microscopy and Nanoengineering)ORCID iD: 0000-0003-1050-8441
AstraZeneca R&D, Med Chem KH471, S-43183 Molndal, Sweden.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Organic Chemistry.
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2016 (English)In: Nature Communications, ISSN 2041-1723, E-ISSN 2041-1723Article in journal (Refereed) Published
Abstract [en]

The first hydrogenation step of benzene, which is endergonic in the electronic ground state (S0), becomes exergonic in the first triplet state (T1). This is in line with Baird’s rule, which tells that benzene is antiaromatic and destabilized in its T1 state and also in its first singlet excited state (S1), opposite to S0, where it is aromatic and remarkably unreactive. Here we utilized this feature to show that benzene and several polycyclic aromatic hydrocarbons (PAHs) to various extents undergo metal-free photochemical (hydro)silylations and transfer-hydrogenations at mild conditions, with the highest yield for naphthalene (photosilylation: 21%). Quantum chemical computations reveal that T1-state benzene is excellent at H-atom abstraction, while COT, aromatic in the T1 and S1 states according to Baird’s rule, is unreactive. Remarkably, also CVD-graphene on SiO2 is efficiently transfer-photohydrogenated using formic acid/water mixtures together with white light or solar irradiation under metal-free conditions.

Place, publisher, year, edition, pages
2016.
National Category
Chemical Sciences Chemical Engineering
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URN: urn:nbn:se:uu:diva-303639DOI: 10.1038/ncomms12962ISI: 000385553900001PubMedID: 27708336OAI: oai:DiVA.org:uu-303639DiVA: diva2:972524
Funder
Wenner-Gren FoundationsSwedish Research CouncilKnut and Alice Wallenberg FoundationÅForsk (Ångpanneföreningen's Foundation for Research and Development)Magnus Bergvall Foundation
Available from: 2016-09-21 Created: 2016-09-21 Last updated: 2016-11-21Bibliographically approved

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