Copper(I)-Dioxygen Reactivity in an Isolated Cavity of Nanoscale Molecular Architecture
Copper(I)-Dioxygen Reactivity in an Isolated Cavity of Nanoscale Molecular Architecture
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纳米级分子结构隔离腔中的铜 (I)-分子氧反应性
DOI：
10.1002/ejic.201800029
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发表时间：
2018
期刊：
影响因子：
--
通讯作者：
and Shinobu Itoh*
中科院分区：
文献类型：
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作者：
Sayantan Paria;Yuma Morimoto;Takehiro Ohta;Hideki Sugimoto;Nobutaka Fujieda;Takashi Ogura;and Shinobu Itoh*
合成并表征了四齿氮配体[CuI（TIPT 3 tren）（CH 3CN）] ClO 4（1）和[CuII（TIPT 3 tren）Cl] BF 4（2）负载的铜（I）和铜（II）配合物，其中TIPT为2，2 ′′，6，6 ′′-四异丙基-1，3 ′：5′，1 ′′-三联苯，tren为三（2-氨乙基）胺.氯化亚铜配合物2具有三角-双锥结构，如通常在tren配体系统中观察到的，其中氯化物配体占据轴向位置，并被封装在由三个TIPT取代基组成的隔离腔中。这种三角-双锥结构在丙酮中是稳定的，其中苯胺基N-H基团与丙酮分子的氧原子之间的氢键相互作用，被捕获在TIPT取代基之间的疏水裂缝中，起着重要的作用。铜（I）络合物1和O2在含丙酮的溶剂中在-110 °C下的反应产生了末端铜（II）超氧化物络合物3和假定的侧边铜（III）过氧化物络合物4，这从变温UV/维斯、共振拉曼和1H和2 H NMR光谱的详细研究中显而易见。DFT计算也验证了3和4的形成。
Copper(I) and copper(II) complexes supported by a bulky tetradentate N4ligand, [CuI(TIPT3tren)(CH3CN)]ClO4(1) and [CuII(TIPT3tren)Cl]BF4(2), were synthesized and characterized, where TIPT is 2,2′′,6,6′′‐tetraisopropyl‐1,3′:5′,1′′‐terphenyl and tren is tris(2‐aminoethyl)amine. The copper(II) chloride complex2exhibits a trigonal‐bipyramidal structure, as usually observed for the tren ligand system, in which the chloride ligand occupies an axial position and is encapsulated in an isolated cavity consisting of three TIPT substituents. Such a trigonal‐bipyramidal structure is stabilized in acetone, in which hydrogen‐bonding interactions between the anilino N–H groups and the oxygen atom of the acetone molecules, entrapped in the hydrophobic clefts between the TIPT substituents, play an important role. The reaction of copper(I) complex1and O2in an acetone‐containing solvent at –110 °C gave end‐on copper(II) superoxide complex3together with putative side‐on copper(III) peroxide complex4, as was evident from detailed studies by variable‐temperature UV/Vis, resonance Raman, and1H and2H NMR spectroscopy. The formation of3and4was also validated by DFT calculations.