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Tellurorhodamine photocatalyzed aerobic oxidation of organo-silanes and phosphines by visible-light

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Abstract

Tellurorhodamine, 9-mesityl-3,6-bis(dimethylamino)telluroxanthylium hexafluorophosphate (1), photocatalytically oxidizes aromatic and aliphatic silanes and triphenyl phosphine under mild aerobic conditions. Under irradiation with visible light, 1 can react with self-sensitized 1O2 to generate the active telluroxide oxidant (2). Silanes are oxidized to silanols and triphenyl phosphine is oxidized to triphenyl phoshine oxide either using 2, or 1 with aerobic irradiation. Kinetic experiments coupled with a computational study elucidate possible mechanisms of oxidation for both silane and phosphine substrates. First-order rates were observed in the oxidation of triphenyl phosphine and methyldiphenyl silane, indicating a substitution like mechanism for substrate binding to the oxidized tellurium(IV). Additionally, these reactions exhibited a rate-dependence on water. Oxidations were typically run in 50 : 50 water/methanol, however, the absence of water decreased the rates of silane oxidation to a greater degree than triphenyl phosphine oxidation. Parallel results were observed in solvent kinetic isotope experiments using D2O in the solvent mixture. The rates of oxidation were slowed to a greater degree in silane oxidation by 2 (kH/kD = 17.30) than for phosphine (kH/kD = 6.20). Various silanes and triphenyl phosphine were photocatalytically oxidized with 1 (5%) under irradiation with warm white LEDs using atmospheric oxygen as the terminal oxidant.

Graphical abstract: Tellurorhodamine photocatalyzed aerobic oxidation of organo-silanes and phosphines by visible-light

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Publication details

The article was received on 01 Feb 2019, accepted on 03 Apr 2019 and first published on 04 Apr 2019


Article type: Paper
DOI: 10.1039/C9DT00487D
Citation: Dalton Trans., 2019, Advance Article

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    Tellurorhodamine photocatalyzed aerobic oxidation of organo-silanes and phosphines by visible-light

    I. D. Rettig, J. Van, J. B. Brauer, W. Luo and T. M. McCormick, Dalton Trans., 2019, Advance Article , DOI: 10.1039/C9DT00487D

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