Dihydrogen Trioxide (HOOOH) Photoelimination from a Platinum(IV) Hydroperoxo-Hydroxo Complex,Journal of the American Chemical Society

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Dihydrogen Trioxide (HOOOH) Photoelimination from a Platinum(IV) Hydroperoxo-Hydroxo Complex
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2014-09-24 , DOI: 10.1021/ja507263f
Lasantha A. Wickramasinghe ₁ , Paul R. Sharp ₁

Affiliation

Photolysis (380 nm) of trans-Pt(PEt3)2(Cl)(OH)(OOH)(4-trifluoromethylphenyl) (1) at -78 °C in acetone-d6 or toluene-d8 yields HOOOH (16-20%) and trans-Pt(PEt3)2(Cl)(4-trifluoromethylphenyl) (2). Also observed in acetone-d6 are H2O2, (CD3)2C(OH)(OOH), and (CD3)2C(OOH)2. Thermal decomposition or room-temperature photolysis of 1 gives O2, water, and 2. Computational modeling (DFT) suggests two intramolecular hydrogen-bonding-dependent triplet pathways for the photolysis and two possible pathways for the thermolysis, one involving proton transfer from the OOH to the OH ligand and the other homolysis of the Pt-OOH bond, abstraction of the OH ligand, and decomposition of the resulting H2O3. Trapping studies suggest the latter pathway.

中文翻译：

三氧化二氢 (HOOOH) 从铂 (IV) Hydroperoxo-Hydroxo 络合物光消除

trans-Pt(PEt3)2(Cl)(OH)(OOH)(4-trifluoromethylphenyl) (1) 在-78 °C 下在丙酮-d6 或甲苯-d8 中的光解 (380 nm) 产生 HOOOH (16-20% ) 和反式 Pt(PEt3)2(Cl)(4-三氟甲基苯基) (2)。在丙酮-d6 中还观察到 H2O2、(CD3)2C(OH)(OOH) 和 (CD3)2C(OOH)2。1 的热分解或室温光解产生 O2、水和 2。计算模型 (DFT) 表明光解有两种依赖于分子内氢键的三重态途径和两种可能的热解途径，一种涉及来自 OOH 的质子转移OH 配体和 Pt-OOH 键的其他均裂，OH 配体的提取，以及所得 H2O3 的分解。诱捕研究表明后一种途径。

更新日期：2014-09-24

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