首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >In situ infrared spectroelectrochemical studies of [Ru6C(CO)(17)] and [Ru6C(CO)(16)](2-): the redox induced conversion of carbon monoxide to carbon dioxide
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In situ infrared spectroelectrochemical studies of [Ru6C(CO)(17)] and [Ru6C(CO)(16)](2-): the redox induced conversion of carbon monoxide to carbon dioxide

机译:[Ru6C(CO)(17)]和[Ru6C(CO)(16)](2-)的原位红外光谱电化学研究:氧化还原诱导一氧化碳转化为二氧化碳

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摘要

Cyclic voltammetry and in situ infrared spectroelectrochemistry and have been used to investigate the redox behaviour of [Ru6C(CO)(17)] and [NBu4](2)[Ru6C(CO)(16)]. Under strictly anaerobic conditions, the electrochemical reduction of [Ru6C(CO)(17)] yields only [Ru6C(CO)(16)](2-). However. in the presence of O-2, the reduction of [Ru6C(CO)(17)] produces 1.1-1.3 mole of CO2 per mole of cluster, in addition to [Ru6C(CO)(16)](2-) and some cluster degradation products. Re-oxidation or electrogenerated [Ru6C(CO)(16)](2-) results in the reformation of [Ru6C(CO)(17)]. The conditions under which oxidation of chemically prepared [Ru6C(CO)(16)](2-) leads to the formation of [Ru6C(CO)(17)] have also been established. The oxidation of [NBu4](2)[Ru6C(CO)(16)](2-) in the absence of a GO-source gives only ill-defined products, as does oxidation in the presence of CO2, such that [Ru6C(CO)(16)](2-) does not scavenge CO from other cluster molecules to form [Ru6C(CO)(17)]. The oxidation of a GO-saturated solution of [NBu4](2)[Ru6C(CO)(16)] produces near quantitative yields of [Ru6C(CO)(17)]. Mechanisms have been proposed to account for these interconversions. [References: 34]
机译:循环伏安法和原位红外光谱电化学,已用于研究[Ru6C(CO)(17)]和[NBu4](2)[Ru6C(CO)(16)]的氧化还原行为。在严格的厌氧条件下,[Ru6C(CO)(17)]的电化学还原仅产生[Ru6C(CO)(16)](2-)。然而。在O-2的存在下,[Ru6C(CO)(17)]的还原除每摩尔[Ru6C(CO)(16)](2-)和一些外,每摩尔簇产生1.1-1.3摩尔的CO2。集群降解产物。再氧化或电产生的[Ru6C(CO)(16)](2-)导致[Ru6C(CO)(17)]的重整。还确定了化学制备的[Ru6C(CO)(16)](2-)氧化导致形成[Ru6C(CO)(17)]的条件。在没有GO源的情况下,[NBu4](2)[Ru6C(CO)(16)](2-)的氧化仅产生不确定的产物,在CO2存在下的氧化也是如此,从而使[Ru6C (CO)(16)](2-)不会从其他簇分子中清除CO形成[Ru6C(CO)(17)]。 [NBu4](2)[Ru6C(CO)(16)]的GO饱和溶液的氧化产生[Ru6C(CO)(17)]接近定量的产率。已经提出了解决这些相互转换的机制。 [参考:34]

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