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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Activation of C-O and C-C bonds and formation of novel HAlOH-ether complexes: An EPR study of the reaction of ground-state Al atoms with methylethyl ether and diethyl ether
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Activation of C-O and C-C bonds and formation of novel HAlOH-ether complexes: An EPR study of the reaction of ground-state Al atoms with methylethyl ether and diethyl ether

机译：C-O和C-C键的活化以及新型HAlOH-醚配合物的形成：基态Al原子与甲基乙基醚和乙醚反应的EPR研究

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Reaction mixtures, containing Al atoms and methylethyl ether (MEE) or diethyl ether (DEE) in an adamantane matrix, were prepared with the aid of a metal-atom reactor known as a rotating cryostat. The EPR spectra of the resulting products were recorded from 77-260 K, at 10 K intervals. Al atoms were found to insert into methyl-O, ethyl-O, and C-C bonds to form CH 3AlOCH 2CH 3, CH _3OAlCH _2CH _3, and CH _3OCH _2AlCH _3, respectively, in the case of MEE while DEE produced CH _3CH _2AlOCH _2CH _3 and CH _3AlCH _2OCH _2CH _3, respectively. From the intensity of the transition lines attributed to the Al atom C-O insertion products of MEE, insertion into the methyl-O bond is preferred. The Al hyperfine interaction (hfi) extracted from the EPR spectra of the C-O insertion products was greater than that of the C-C insertion products, that is, 5.4% greater for the DEE system and 7% greater for the MEE system. The increase in Al hfi is thought to arise from the increased electron-withdrawing ability of the substituents bonded to Al. Besides HAlOH, resulting from the reaction of Al atoms with adventitious water, novel mixed HAlOH:MEE and HAlOH:DEE complexes were identified with the aid of isotopic studies involving H _2 ~(17)O and D _2O. The Al and H hfi of HAlOH were found to decrease upon complex formation. These findings are consistent with the nuclear hfi calculated using a density functional theory (DFT) method with close agreement between theory and experiment occurring at the B3LYP level using a 6-311+G(2df,p) basis set.
机译：借助金属原子反应器（称为旋转低温恒温器），制备在金刚烷基质中含有Al原子和甲基乙基醚（MEE）或二乙基醚（DEE）的反应混合物。所得产品的EPR光谱以10 K间隔记录在77-260 K之间。对于MEE，而DEE产生CH _3CH _2AlOCH _2CH，发现Al原子分别插入甲基O，乙基O和CC键以形成CH 3AlOCH 2CH 3，CH _3OAlCH _2CH _3和CH _3OCH _2AlCH _3。 _3和CH _3AlCH _2OCH _2CH _3。从归因于MEE的Al原子C-O插入产物的过渡线的强度，优选插入甲基-O键。从C-O插入产物的EPR光谱中提取的Al超精细相互作用（hfi）大于C-C插入产物的Al，即DEE系统的5.4％和MEE系统的7％。 Al hfi的增加被认为是由于键合到Al上的取代基的吸电子能力增强所致。除了由Al原子与不定水反应产生的HAlOH外，借助涉及H _2〜（17）O和D _2O的同位素研究，还鉴定出了新型的HAlOH：MEE和HAlOH：DEE混合复合物。发现HAlOH的Al和H hfi在复合物形成时降低。这些发现与使用密度泛函理论（DFT）方法计算的核hfi一致，理论和实验之间的吻合紧密，发生在B3LYP级别，使用6-311 + G（2df，p）基集。

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