Superoxo, peroxo, and hydroperoxo complexes formed from reactions of rhodium porphyrins with dioxygen: thermodynamics and kinetics.
Superoxo, peroxo, and hydroperoxo complexes formed from reactions of rhodium porphyrins with dioxygen: thermodynamics and kinetics.
复制标题
铑卟啉与双氧反应形成的超氧、过氧和氢过氧复合物：热力学和动力学。
DOI：
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发表时间：
2006
影响因子：
15
通讯作者：
B. Wayland
中科院分区：
文献类型：
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作者：
Weihong Cui;B. Wayland
Rh(II)与氧反应生成末端超氧和桥联双过氧基配合物。本文报道了四甲基卟啉(TMP)Rh*和间-二甲基系联二茂铁(*Rh(m-xylyl)Rh*)与氧形成络合物的平衡常数。(TMP)Rh-H与氧反应生成瞬时氢过氧络合物((TMP)Rh-OHO)，再与之反应生成Rh(II)络合物((TMP)Rh*)和水。(TMP)Rh-H与O2反应的动力学研究表明，氧与(TMP)Rh-H单元几乎一致地加成。本文报道了H_2/O_2和CH_4/O_2的混合物与~*Rh(m-二甲基)Rh~*的反应活性。
Rhodium(II) porphyrin complexes react with dioxygen to form terminal superoxo and bridged mu-peroxo complexes. Equilibrium constants for dioxygen complex formation with rhodium(II) tetramesitylporphyrin ((TMP)Rh*) and a m-xylyl-tethered dirhodium(II) diporphyrin complex (*Rh(m-xylyl)Rh*) are reported. (TMP)Rh-H reacts with oxygen to form a transient hydroperoxy complex ((TMP)Rh-OOH), which reacts on to form the rhodium(II) complex ((TMP)Rh*) and water. Kinetic studies for reactions of (TMP)Rh-H with O2 suggest a near concerted addition of dioxygen to the (TMP)Rh-H unit. Reactivity studies for mixtures of H2/O2 and CH4/O2 with the dirhodium(II) complex (*Rh(m-xylyl)Rh*) are reported.