Ultraviolet irradiation of the peroxo-complexes [Ti(O2)(tpp)] and [Mo(O2)(tpp)](tpp = 5,10,15,20-tetraphenylporphyrinate) induces elimination of O2 and generation of the corresponding oxometalloporphyrins [TiO(tpp)] and [MoO(tpp)]. Reductive elimination of O2 from [Fe(tpp)}2O] also occurs upon irradiation of argon-purged solutions. Studies using spin traps in e.s.r. experiments, together with quenching
过
氧配合物[Ti(O 2)(tpp)]和[Mo(O 2)(tpp)](tpp = 5,10,15,20-
四苯基卟啉)的紫外线辐照可消除O 2并生成O 2相应的含
氧金属
卟啉[TiO(tpp)]和[MoO(tpp)]。从[Fe(tpp)} 2 O]中还原O 2也会在
氩气吹扫的溶液中发生。研究使用自旋捕捉在ESR实验中,淬火实验一起,指示peroxocomplexes的光解产生Ó 2在1 Δ克激发态。对于[Fe(tpp)} 2 O],结果因所用条件而异。在充气的CH 2 Cl中在2种溶液中,在O 2激发态的淬灭过程中产生1 O 2。在
脱气CH 2
氯2个解决方案显然1 Ò 2没有在光诱导
脱氧反应形成的,而是,使用旋陷阱ESR调查研究表明形成的超
氧离子Ò 2 - 。还讨论了1 O 2和光生O 2对溶剂的侵蚀-涉及自由基的形成。