Dalton Transactions p. 5665 - 5673 (2019)
Update date:2022-08-11
Topics:
Rettig, Irving D.
Van, Jackson
Brauer, Jacob B.
Luo, Wentai
McCormick, Theresa M.
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.
View MoreBaoding City Light Industry And Textiles Imp.& Exp. Corp. Chemical Department.
Contact:86-312-3262436
Address:NO.658 CHAOYANG SOUTH STREET,BAODING CITY HEBEI CHINA
NINGBO PANGS CHEM INT’L CO.,LTD.
Contact:+86-574-27666845
Address:FLOOR 21,BUILDING NO.11,XIN TIAN DI,NO.689 SHI JI ROAD,NINGBO CHINA
SHIJIAZHUANG KAIZHENG TRADING CO.,LTD
Contact:86-311-68075739
Address:1-1-818 lemo building,No.18 north of Pingan street,Qiaodong district,Shiajiazhuang.
zhangjiagang bonded areas banggao co;ltd
website:http://www.shunchangchem.com
Contact:0086-13921972933
Address:Dongsha Chemical Zone.Zhangjiagang, Jiangsu Province
ShangHai Ruiyi Medical Technology Co.,Ltd.
Contact:+86-21-54718086
Address:No951 Jianchuan RD,Minhang District
Doi:10.1246/bcsj.62.339
(1989)Doi:10.1021/ja305360q
(2012)Doi:10.1016/S0022-328X(98)00974-7
(1999)Doi:10.1039/a708742j
(1998)Doi:10.1016/j.saa.2020.118657
(2020)Doi:10.1021/ja00217a006
(1988)