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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Spectroscopic characterization of the oxo-transfer reaction from a bis(mu-oxo)dicopper(III)complex to triphenylphosphine
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Spectroscopic characterization of the oxo-transfer reaction from a bis(mu-oxo)dicopper(III)complex to triphenylphosphine

机译：从双（mu-oxo）二铜（III）配合物到三苯基膦的羰基转移反应的光谱表征

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The oxygen-atom transfer reaction from the bis(mu-oxo)dicopper(III)complex [Cu~(1II)2(mu-O)_2(L)_2]~(2+)1,where L = N,N,N',N'-tetraethylethylenediamine,to PPH_3 has been studied by UV-vis,EPR,~1H NMR and Cu K-edge X-ray absorption spectroscopy in parallel at low temperatures(193 K)and above.Under aerobic conditions(excess dioxygen),1 reacted with PPH_3,giving O=PPH_3 and a diamagnetic species that has been assigned to an oxo-bridged dicopper(II)complex on the basis of EPR and Cu K-edge X-ray absorption spectroscopic data.Isotope-labeling experiments(~(18)O_2)established that the oxygen atom incorporated into the triphenylphosphine oxide came from both complex 1 and exogenous dioxygen.Detailed kinetic studies revealed that the process is a third-order reaction;the rate law is first order in both complex 1 and triphenylphosphine,as well as in dioxygen.At temperatures above 233 K,reaction of 1 with PPH_3 was accompanied by ligand degradation,leading to oxidative N-dealkylation of one of the ethyl groups.By contrast,when the reaction was performed in the absence of excess dioxygen,negligible substrate(PPH_3)oxidation was observed.Instead,highly symmetrical copper complexes with a characteristic isotropic EPR signal at g = 2.11 were formed.These results are discussed in terms of parallel reaction channels that are activated under various conditions of temperature and dioxygen.
机译：双（μ-氧代）双铜（III）络合物[Cu〜（1II）2（mu-O）_2（L）_2]〜（2+）1的氧原子转移反应，其中L = N，N在有氧条件下（193 K）及更高温度下，通过紫外可见光谱，EPR，〜1H NMR和Cu K-edge X射线吸收光谱研究了PPH_3中的N，N'，N'-四乙基乙二胺对PPH_3的影响。过量的双氧），1与PPH_3反应，给出O = PPH_3，并根据EPR和Cu K边X射线吸收光谱数据将反磁性物质分配给氧桥双铜（II）络合物。标记实验（〜（18）O_2）证实结合到三苯膦氧化物中的氧原子来自复合物1和外源性双氧。详细的动力学研究表明，该过程是三阶反应;速率定律均为三阶。在高于233 K的温度下，1与PPH_3的反应伴随着配体的降解，导致t之一的氧化N-脱烷基化。相比之下，当反应在没有过量双氧的情况下进行时，观察到可忽略的底物（PPH_3）氧化。相反，形成了高度对称的铜配合物，其特征性各向同性EPR信号在g = 2.11时。这些结果是关于在不同温度和双氧条件下活化的平行反应通道的讨论。

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