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首页> 外文期刊>Chemistry: A European journal >C-C versus C-H Activation and versus Agostic C-C Interaction Controlled by Electron Density at the Metal Center
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C-C versus C-H Activation and versus Agostic C-C Interaction Controlled by Electron Density at the Metal Center

机译：C-C与C-H活化以及金属中心电子密度控制的Ag-CC相互作用

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摘要

Based on the PCN ligand 2,a remarkable degree of control over C-C versus C-H bond activation and versus formation of an agostic C-C complex was demonstrated by choice of cationic [Rh(CO)_n(C_2H_4)_2-N](n=o,1,2)precursors.Whereas reaction of 2 with [Rh(C_2h_4)_2(solv)_n]BF_4 results in exclusive C-C bond activation to yield product 5,reaction with the dicarbonyl precursor[Rh(CO)_2(solv)_n]BF_4 leads to formation of the C-H activated complex 9.The latter process is promoted by intramolecular deprotonation of the C-H bond by the bemilabile amine arm of the PCN ligand.The mixed monocarbonyl monoethylene Rh species[Rh(CO)(C_2h_4)]BF_4 reacts with the PCN ligand 2 to give an agostic complex 7.The C-C activated complex 5 is easily converted to the C-H activated one (9) by reaction with CO;the reaction proceeds by a unique sequence of 1,2-metalto-carbon methyl shift,agostic interaction,and C-H activation processes.Similarly,the C-C agostic complex 7 is converted to the same C-H activated product 9 by treatment with CO.
机译：基于PCN配体2，通过选择阳离子[Rh（CO）_n（C_2H_4）_2-N]（n = o， 1,2）前体。而2与[Rh（C_2h_4）_2（solv）_n] BF_4的反应导致独有的CC键活化，生成产物5，与二羰基前体[Rh（CO）_2（solv）_n]反应BF_4导致CH活化的配合物9的形成.PCN配体的易分解胺臂使CH键的分子内去质子化促进了后者的过程。与PCN配体2产生柔和的络合物7. CC活化的络合物5通过与CO反应很容易转化为CH活化的化合物（9）;反应通过独特的1,2-金属-碳-甲基转移顺序进行，声光相互作用和CH活化过程。类似地，CC原子团7被转化为相同的CH活化产物ct 9用CO处理。

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