钌（II）卟啉醌卡宾配合物：卡宾转移和氢原子转移反应的合成、晶体结构和反应性,Journal of the American Chemical Society

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钌（II）卟啉醌卡宾配合物：卡宾转移和氢原子转移反应的合成、晶体结构和反应性
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-05-08 , DOI: 10.1021/jacs.9b03357
Hai-Xu Wang ₁ , Qingyun Wan ₁ , Kai Wu ₁ , Kam-Hung Low ₁ , Chen Yang ₁ , Cong-Ying Zhou ₁ , Jie-Sheng Huang ₁ , Chi-Ming Che _{1,

2}

Affiliation

新型金属卡宾配合物的反应性研究可为催化卡宾转移反应以及其他合成方案提供新的机会。具有醌型卡宾 (QC) 配体的金属配合物被认为是使用重氮醌的各种金属催化 QC 转移反应的关键中间体，这需要开发表征良好的金属-QC 配合物的 QC 转移化学。在此，我们报告了钌卟啉 [Ru(Por)(QC)] 的分离和 QC 转移，这有助于 (i) 结构表征的金属-QC 复合物（通过 X 射线晶体学）和（ii）分离的金属-QC进行 QC 转移反应的复合物。复合物 [Ru(Por)(QC)] 由 [Ru(Por)(CO)] 与重氮醌反应制备，并表现出双重反应性，即氢原子转移 (HAT) 以及 QC 转移。从这些 Ru-QC 配合物到亚硝基芳烃 (ArNO) 的化学计量 QC 转移反应以高达 90% 的产率提供了硝酮，并且还开发了相应的催化反应。一系列带有给电子和吸电子取代基的 QC 配体的化学计量和催化反应均显示出对 QC 转移反应性的反向取代基效应。配合物 [Ru(Por)(QC)] 也对 CH 和 XH (X = N, S) 键具有反应性，可以催化 1,4-环己二烯的有氧氧化；他们与不饱和烃的化学计量 HAT 反应产生高达 88% 的产物产率。通过光谱方法和密度泛函理论 (DFT) 计算研究了 [Ru(Por)(QC)] 独特的双反应性和电子特征。从这些 Ru-QC 配合物到亚硝基芳烃 (ArNO) 的化学计量 QC 转移反应以高达 90% 的产率提供了硝酮，并且还开发了相应的催化反应。一系列带有给电子和吸电子取代基的 QC 配体的化学计量和催化反应均显示出对 QC 转移反应性的反向取代基效应。配合物 [Ru(Por)(QC)] 对 CH 和 XH (X = N, S) 键也具有反应性，可以催化 1,4-环己二烯的有氧氧化；他们与不饱和烃的化学计量 HAT 反应产生高达 88% 的产物产率。通过光谱方法和密度泛函理论 (DFT) 计算研究了 [Ru(Por)(QC)] 独特的双反应性和电子特征。从这些 Ru-QC 配合物到亚硝基芳烃 (ArNO) 的化学计量 QC 转移反应以高达 90% 的产率提供了硝酮，并且还开发了相应的催化反应。一系列带有给电子和吸电子取代基的 QC 配体的化学计量和催化反应均显示出对 QC 转移反应性的反向取代基效应。配合物 [Ru(Por)(QC)] 也对 CH 和 XH (X = N, S) 键具有反应性，可以催化 1,4-环己二烯的有氧氧化；他们与不饱和烃的化学计量 HAT 反应产生高达 88% 的产物产率。通过光谱方法和密度泛函理论 (DFT) 计算研究了 [Ru(Por)(QC)] 独特的双反应性和电子特征。

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Ruthenium(II) Porphyrin Quinoid Carbene Complexes: Synthesis, Crystal Structure and Reactivity Towards Carbene Transfer and Hydrogen Atom Transfer Reactions

Reactivity study of novel metal carbene complexes can offer new opportunities in catalytic carbene transfer reactions as well as in other synthetic protocols. Metal complexes with quinoid carbene (QC) ligands are assumed to be key intermediates in a variety of metal-catalyzed QC transfer reactions using diazo quinones, which demands development of the chemistry of QC transfer of well characterized metal-QC complexes. Herein we report the isolation and QC transfer of ruthenium porphyrins [Ru(Por)(QC)] which contribute the first examples of (i) structurally characterized metal-QC complex (by X-ray crystallography) and (ii) isolated metal-QC complex that undergoes QC transfer reaction. The complexes [Ru(Por)(QC)] were prepared from reaction of [Ru(Por)(CO)] with diazo quinones and exhibited dual reactivity, i.e., hydrogen atom transfer (HAT) as well as QC transfer. The stoichiometric QC transfer reactions from these Ru-QC complexes to nitrosoarenes (ArNO) afforded nitrones in up to 90% yield, and the corresponding catalytic reactions were also developed. Both the stoichiometric and catalytic reactions for a series of QC ligands bearing electron-donating and -withdrawing substituents showed a reverse substituent effect on the QC transfer reactivity. Complexes [Ru(Por)(QC)] are also reactive toward C-H and X-H (X = N, S) bonds and can catalyze aerobic oxidation of 1,4-cyclohexadiene; their stoichiometric HAT reactions with unsaturated hydrocarbons gave product yields of up to 88%. The unique dual reactivity and electronic feature of [Ru(Por)(QC)] were studied by spectroscopic means and density functional theory (DFT) calculations.

更新日期：2019-05-08

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