PHOTOINDUCED ELECTRON-TRANSFER REACTIONS OF TRANSITION-METAL COMPLEXES WITH AMINES - MECHANISTIC STUDIES OF ALTERNATE PATHWAYS TO BACK ELECTRON-TRANSFER
PHOTOINDUCED ELECTRON-TRANSFER REACTIONS OF TRANSITION-METAL COMPLEXES WITH AMINES - MECHANISTIC STUDIES OF ALTERNATE PATHWAYS TO BACK ELECTRON-TRANSFER
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DOI：
10.1021/ja00537a037
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发表时间：
1980-01-01
影响因子：
15
通讯作者：
WHITTEN, DG
中科院分区：
文献类型：
--
作者：
DELAIVE, PJ;FOREMAN, TK;WHITTEN, DG
研究了胺对Ru(II)、Fe(II)多吡啶络合物的光还原作用。被研究的两个Ru(II)络合物在无水介质中三乙胺存在的情况下被发现在辐照下发生“永久性”还原，而被研究的两个铁配合物和(Bpy)_3Ru1I~(2+)被发现不具有永久性还原。尽管如此，所有研究的络合物都被发现在水存在下进行辐射时产生乙醛，这表明三乙胺正在发生不可逆氧化。对亚硝基硬烯等自旋陷阱的研究也导致了对来自三乙胺和AVV-二甲基苯胺的烷基的拦截。自旋捕获和产物研究相结合，指出了一种机制，即在初始电子转移猝灭步骤中形成的胺自由基阳离子与第二个胺分子快速反应，得到烷基自由基，其命运随后由所涉及的特定金属络合物的性质和氧化还原行为决定。
A study of the photoreduction of polypyridyl complexes of ruthenium (II) and iron (II) by amines is reported. While two of the ruthenium (II) complexes studied are found to give “permanent” reduction on irradiation in thepresence of triethylamine in anhydrous media, the two iron complexes studied and (bpy) 3Ru1I2+ are found not to give a permanent reduction. Nonetheless, all complexes studied are found to give acetaldehyde when irradiation is carried out in the presence of water, suggesting that an irreversible oxidation of triethylamine is taking place. Studies with spin traps such as nitrosodurene also result in interception of alkyl radicals derived from triethylamine and AVV-dimethylaniline. The combination of spin trapping and product studies points to a mechanism in which the amine radical cation formed in the initial electron transfer quenching step rapidly reacts with a second molecule of amine to give an alkyl radical whose fate is subsequently determined by the properties and redox behavior of the specific metal complex involved.