O-Atom Exchange between H2O and CO2 Mediated by a Bis(dithiolene)tungsten Complex

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• 作者：Junhyeok Seo ; Eunsuk Kim
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：August 6, 2012
• 年：2012
• 卷：51
• 期：15
• 页码：7951-7953
• 全文大小：210K
• 年卷期：v.51,no.15(August 6, 2012)
• ISSN：1520-510X

文摘

Inspired by the CO₂-reductatse activity of tungsten-dependent formate dehydrogenases (W-FDHs), a reduced W-FDH model, [W^IV(OH)(S₂C₂Ph₂)₂]^{鈭?/sup>, was prepared in situ through hydrolysis of [WIV(OPh)(S₂C₂Ph₂)₂]鈭?/sup> (1) and its reactivity with CO₂ was investigated. The reaction between [WIV(OH)(S₂C₂Ph₂)₂]鈭?/sup> and CO₂ at room temperature leads to the formation of [WIV(O)(S₂C₂Ph₂)₂]2鈥?/sup> (2), which slowly oxidizes to [WV(O)(S₂C₂Ph₂)₂]鈭?/sup> (3). Isotopic labeling experiments reveal that the O atom in CO₂ incorporates into 3. This implies that there is carbonic anhydrase like activity, in which carbonation and decarboxylation are mediated by a bis(dithiolene)tungsten complex.}