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首页> 外文期刊>Chemistry: A European journal >Synthesis and Redox Behavior of Ruthenocene-Terminated Oligoenes:Characteristic and Stable Two-Electron Redox System and Lower Potential Shift of the Two-Electron Oxidation Wave with Elongating Conjugation
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Synthesis and Redox Behavior of Ruthenocene-Terminated Oligoenes:Characteristic and Stable Two-Electron Redox System and Lower Potential Shift of the Two-Electron Oxidation Wave with Elongating Conjugation

机译：钌茂金属封端的低聚烯烃的合成及氧化还原行为：特性稳定的双电子氧化还原体系和双电子氧化波在扩展共轭作用下的较低电位漂移

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Ruthenocene-terminated bu tadienes and hexatrienes were prepared by the Wittig reaction of 3-ruthe-nocenyl-2-propenals with ruthenocenyl-methylphosphonium salts and the Mu-kaiyama coupling of the propenals,respectively.Cyclic voltammetry of these complexes indicated that they were in volved in a stable two-electron redox process.The oxidation potentials for ruthenocene-to ligoenes shifted progressively to lower potential with the increasing CH=CH units as follows:Rc-Rc (0.32 V)>RcCH=CHRc (+0.09 V)>Rc(CH=CH)_2Rc (-0.06 V)>Rc(CH=CH)_3Rc (-0.07 V),(Rc=ruthenocene).The tendency is in remarkable contrast to that in the successive one-electron redox process.These complexes were chemically oxidized to give stable crystalline solids,whose structures were confirmed by NMR spectroscopy and X-ray analysis to be oligoene analogues of a bis(ful-vene) complex,for example,[(eta~5-C_sMe_5)Ru{mu_2-eta~6:eta~6-C_5H_4CH(CH=CH)_n-CHC_5H_4}Ru(eta~5-C_5Me_5)]~(2+) (n=1 or 2).The DFT calculation of the two-electron-oxidized species reproduced well the fulvene-complex structure for the ruthenocene moieties.Since both the neutral and oxidized species are stable and chemically reversible,this redox system may be serviceable as a two-electron version of the ferrocene one-electron redox system.
机译：钌茂茂封端的丁二烯和己三烯是通过3-钌钌烯基-2-丙烯醛与钌茂烯基甲基phosph盐的Wittig反应和丙烯腈的Mu-kaiyama偶联制备的。这些化合物的循环伏安法表明它们处于稳定的双电子氧化还原过程，随着CH = CH单元的增加，钌茂金属到Ligoenes的氧化电势逐渐转移到较低电势，如下所示：Rc-Rc（0.32 V）> RcCH = CHRc（+0.09 V）> Rc（CH = CH）_2Rc（-0.06 V）> Rc（CH = CH）_3Rc（-0.07 V），（Rc =钌茂铁），这种趋势与连续的单电子氧化还原过程形成了鲜明的对比。将配合物化学氧化，得到稳定的结晶固体，其结构已通过NMR光谱和X射线分析证实为双（富烯）配合物的低聚类似物，例如[[eta〜5-C_sMe_5）Ru {mu_2 -eta〜6：eta〜6-C_5H_4CH（CH = CH）_n-CHC_5H_4} Ru（eta〜5-C_5Me_5）]〜（2+）（n = 1或2）.two-e的DFT计算电子氧化物种很好地再现了钌茂金属部分的富烯复杂结构。由于中性和氧化物种均稳定且化学可逆，因此该氧化还原体系可用作二茂铁单电子氧化还原体系的两电子版本。

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