NaClO-Generated Iron(IV)oxo and Iron(V)oxo TAMLs in Pure Water.
NaClO-Generated Iron(IV)oxo and Iron(V)oxo TAMLs in Pure Water.
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DOI：
10.1021/jacs.6b09572
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发表时间：
2016-10-26
影响因子：
15
通讯作者：
Collins TJ
中科院分区：
文献类型：
--
作者：
Mills MR;Weitz AC;Hendrich MP;Ryabov AD;Collins TJ
全脂肪族TAML活化剂[FeIII{(Me2CNCOCMe2NCO)2CMe2}-OH2]−(3)的独特性质，即增加了配体的空间体积和对酸诱导的脱金属反应具有无与伦比的抵抗力，使其能够在任何pH的纯水中生成高价铁衍生物。在pH值为2到10.6的范围内，NaClO很容易生成铁(V)氧物种，而没有任何可观察到的中间体。这是第一个报道的铁(V)氧在纯水中形成的例子。在pH为13时，不生成铁(V)氧，而NaClO将3氧化成铁(IV)氧衍生物。
The unique properties of entirely aliphatic TAML activator [FeIII{(Me2CNCOCMe2NCO)2CMe2}-OH2]− (3), namely the increased steric bulk of the ligand and the unmatched resistance to the acid-induced demetalation, enables the generation of high-valent iron derivatives in pure water at any pH. An iron(V)oxo species is readily produced with NaClO at pH values from 2 to 10.6 without any observable intermediate. This is the first reported example of iron(V)oxo formed in pure water. At pH 13, iron(V)oxo is not formed and NaClO oxidizes 3 to an iron(IV)oxo derivative.