Metal-free photochemical silylations and transfer hydrogenations of benzenoid hydrocarbons and graphene

Raffaello Papadakis, Hu Li, Joakim Bergman, Anna Lundstedt, Kjell Jorner, Rabia Ayub, Soumyajyoti Haldar, Burkhard O. Jahn, Aleksandra Denisova, Burkhard Zietz, Roland Lindh, Biplab Sanyal, Helena Grennberg, Klaus Leifer and Henrik Ottosson ()
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Raffaello Papadakis: Department of Chemistry—Ångström Laboratory
Hu Li: Applied Materials Science, Uppsala University
Joakim Bergman: AstraZeneca R&D Mölndal, Medicinal Chemistry-KH471
Anna Lundstedt: Uppsala University
Kjell Jorner: Department of Chemistry—Ångström Laboratory
Rabia Ayub: Department of Chemistry—Ångström Laboratory
Soumyajyoti Haldar: Uppsala University
Burkhard O. Jahn: Uppsala University
Aleksandra Denisova: Department of Chemistry—Ångström Laboratory
Burkhard Zietz: Department of Chemistry—Ångström Laboratory
Roland Lindh: Department of Chemistry—Ångström Laboratory
Biplab Sanyal: Uppsala University
Helena Grennberg: Uppsala University
Klaus Leifer: Applied Materials Science, Uppsala University
Henrik Ottosson: Department of Chemistry—Ångström Laboratory

Nature Communications, 2016, vol. 7, issue 1, 1-10

Abstract: Abstract 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 cyclooctatetraene, 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.

Date: 2016
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DOI: 10.1038/ncomms12962

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