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首页> 外文期刊>Chemistry: A European journal >Quantitative Evaluation of d-pi Interaction in Copper(I)Complexes and Control of Copper(I)-dioxygen Reactivity
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Quantitative Evaluation of d-pi Interaction in Copper(I)Complexes and Control of Copper(I)-dioxygen Reactivity

机译：铜（I）络合物中d-pi相互作用的定量评估和铜（I）-二氧反应性的控制

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摘要

Crystal structures of the copper(I)complexes 1~X,2,and 3 of a series of tridentate ligands L1~X,L2,and L3,respectively (L1~X:p-substituted derivatives of N,N-bis[2-(2-pyridyl)ethyl]-2-phenylethylamine:X=H,Me,OMe,Cl,NO_2;L2:N,N-bis[2-(2-pyridyl)ethyl]-2-methyl-phenylethylamine;L3:N,N-bis[2-(2-pyridyl)ethyl]-2,2-diphenylethylamine)were solved to demonstrate that all the copper(I)complexes involve an eta~2 copper-arene interaction with the phenyl ring of the ligand sidearm.The Cu~I ion in each complex has a distorted tetrahedral geometry consisting of the three nitrogen atom (one tertiary amine nitrogen atom and two pyridine nitrogen atoms)and C_1-C_2 of the henyl ring of ligand sidearm,whereby the Cu-C distances of the copper-arene interaction significantly depend on the para substituents.The existence of the copper-arene interaction in a nonpolar organic solvent (CH_2Cl_2)was demonstrated by the observation of an intense MLCT band around 290 nm,an the magnitude of the interaction of the ~1H and ~(13)C NMR spectra and the redox potentials E_(1/2)of the copper ion,as well as by means of the ligand-exchange rection between the phenyl ring and CH_3CN as an external ligand.the thermodynamic parameters DELTAH~o and DELTAS~o for th ligand-exchange reaction with CH_3CN afforded a quantitative measure for the energy difference of the copper-arene interaction in the series of copper(I)coplexes.Density functional studies indicated that the copper(I)-arene interaction mainly consists of the interaction between the d_(z~2)orbital of Cu~I and a pi orbital of the phenyl ring.The copper(I)complexes 1~X reacted with O_2 at -80deg C in CH_2Cl_2 to give the correspodning (mu-eta~2:eta~2-peroxo)dicopper(II)complexes 4,he formation rates k_(obs)of which were significantly retarded by stronger d-pi interaction,while complexes 2 and 3,which exhibit the strongest d-pi interaction showed signifciantly lower reactivity toward O_2 under the same experimental conditions.Thus,the d-pi interaction has been demonstrated for the first time to affect the copper(I)-dioxygen rectiity,adn represents a new aspects of ligand effects in copper(I)-dioxygen chemistry.
机译：铜（I）的晶体结构分别是一系列三齿配体L1〜X，L2和L3的1〜X，2和3（L1〜X：N，N-bis [2的对位取代衍生物-（2-吡啶基）乙基] -2-苯基乙胺：X = H，Me，OMe，Cl，NO_2; L2：N，N-双[2-（2-吡啶基）乙基] -2-甲基-苯基乙胺; L3 ：N，N-双[2-（2-吡啶基）乙基] -2，2-二苯基乙胺）经解析证明所有的铜（I）配合物都与η-铜的芳环发生η〜2铜-芳烃相互作用。每个络合物中的Cu〜I离子具有扭曲的四面体几何形状，由四个氮原子（一个叔胺氮原子和两个吡啶氮原子）和配位体侧链烯环的C_1-C_2组成，其中Cu-铜-芳烃相互作用的C距离很大程度上取决于对位取代基。通过观察到约290 nm的强MLCT谱带，可以观察到非极性有机溶剂（CH_2Cl_2）中铜-芳烃相互作用的存在。的相互作用〜1H和〜（13）C NMR光谱以及铜离子的氧化还原电势E_（1/2），以及通过苯环与作为外部配体的CH_3CN之间的配体交换反应。 DELTAH_o和DELTAS_o与CH_3CN进行配体交换反应，定量测量了一系列铜（I）配合物中铜-芳烃相互作用的能量差，密度泛函研究表明，铜（I）-芳烃相互作用主要由Cu〜I的d_（z〜2）轨道与苯环的pi轨道之间的相互作用组成。铜（I）配合物1〜X在-80°C下于CH_2Cl_2中与O_2反应，得到对应于（mu-eta〜2：eta〜2-过氧）双铜（II）的配合物4，其形成速率k_（obs）被较强的d-pi相互作用显着阻碍，而配合物2和3表现出最强的相互作用在相同的实验条件下，d-pi相互作用对O_2的反应性显着降低。因此，d-pi相互作用n首次被证明会影响铜（I）-双氧的平直度，adn代表了铜（I）-双氧化学中配体效应的新方面。

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