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首页> 外文期刊>International Journal of Electrochemical Science >Oxidatively-Promoted CO-Substitution Reaction by PPh3 in the Dinuclear FvCo2(CO)4 in Low-Polarity Media Comprising CH2Cl2/[NBu4][B(C6F5)4]
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Oxidatively-Promoted CO-Substitution Reaction by PPh3 in the Dinuclear FvCo2(CO)4 in Low-Polarity Media Comprising CH2Cl2/[NBu4][B(C6F5)4]

机译：在含CH 的低极性介质中，PPh 3 在双核FvCo 2 （CO） 4 中的氧化促进CO取代反应2 Cl 2 / [NBu 4 ] [B（C 6 F 5 ） 4 ]

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Electrochemically-promoted CO-substitution of FvCo2(CO)4, 1, by using PPh3 in media composing ofCH2Cl2 and the weakly coordinating [NBu4][B(C6F5)4] electrolyte has been achieved on both cyclicvoltammetry (CV) and bulk electrolysis time scales. Using CV and in the presence of 1 equiv of PPh3,the substitution reaction is very simple, leading to the stable mono-substituted product,+ + [FvCo2(CO)3PPh3] , 2 , which can be either reversibly oxidized (E1/2 = 0.2 V) to the mono-substituted2+ 2+ dication, [FvCo2(CO)3PPh3] , 2 , or reduced to the neutral FvCo2(CO)3PPh3, 2 at E1/2 = -0.35 V vs0/+ Fc . Generation of these substitution products in the bulk electrolysis time scale allowed for facilemeasurements of their spectroscopic properties via IR and ESR spectroscopy. IR data revealed that the2+ final product of the oxidative bulk electrolysis is the monosubstituted dication, 2 , with IR bands at 2+ + 2114, 2091 and 2063 cm . One-electron back-reduction of 2 to 2 allowed for spectral identification+ of the radical monocation via IR and ESR. The fluid and frozen ESR spectra of 2 are in a goodagreement with its IR data and consistent with having a transoid configuration. Finally, the neutral-1 monosubstituted, 2, gave IR bands confirming the presence of one Co(CO)(PPh3) moiety at 1925cm-1 and one Co(CO)2 group at 2022 and 1958 cm , respectively. Importantly, this work clearlydemonstrates that "electrochemical switch" approach can be applied to undertake and probe CO- substitution by the stronger PPh3 nucleophile for the dinuclear FvCo2(CO)4 system. This significantoutcome is made possible by the greatly enhanced stability of the generated radical cations of 1 inmedia comprising gentle solvent and supporting electrolyte.
机译：在循环伏安法（CV）和本体电解时间上，通过在PPCH3与CH2Cl2和弱配位[NBu4] [B（C6F5）4]电解质组成的介质中使用PPh3，电化学促进了FvCo2（CO）4，1，的CO取代秤。使用CV并在1当量的PPh3存在下，取代反应非常简单，得到稳定的单取代产物+ + [FvCo2（CO）3PPh3] 2，该产物可被可逆氧化（E1 / 2 （FvCo2（CO）3PPh3] 2或还原为中性FvCo2（CO）3PPh3 2在E1 / 2 = -0.35 V vs0 / + Fc时）。这些取代产物在大量电解时间尺度上的产生允许通过IR和ESR光谱法容易地测量其光谱性质。红外数据显示，氧化本体电解的2+最终产物是单取代的离子2，在2+ + 2114、2091和2063 cm处具有IR带。 1至2的单电子反向还原可通过IR和ESR对自由基单阳离子进行光谱识别+。 2的流体和冰冻ESR光谱与其IR数据非常吻合，并且与反式结构一致。最后，中性-1单取代2产生IR谱带，分别确认在2025和1958 cm处存在一个Co（CO）（PPh3）部分和一个在Co22中存在一个Co（CO）2基团。重要的是，这项工作清楚地表明，“电化学转换”方法可用于通过双核FvCo2（CO）4系统用较强的PPh3亲核试剂进行和取代CO取代。通过显着提高包含温和溶剂和支持电解质的1种中间产物产生的自由基阳离子的稳定性，使这一重大成果成为可能。

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