Anion-Receptor Mediated Oxidation of Carbon Monoxide to Carbonate by Peroxide Dianion
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- 作者：Matthew Nava ; Nazario Lopez ; Peter M眉ller ; Gang Wu ; Daniel G. Nocera ; Christopher C. Cummins
- 刊名：Journal of the American Chemical Society
- 出版年：2015
- 出版时间：November 25, 2015
- 年：2015
- 卷：137
- 期：46
- 页码：14562-14565
- 全文大小：291K
- ISSN：1520-5126
文摘
The reactivity of peroxide dianion O22鈥?/sup> has been scarcely explored in organic media due to the lack of soluble sources of this reduced oxygen species. We now report the finding that the encapsulated peroxide cryptate, [O2鈯?i>mBDCA-5t-H6]2鈥?/sup> (1), reacts with carbon monoxide in organic solvents at 40 掳C to cleanly form an encapsulated carbonate. Characterization of the resulting hexacarboxamide carbonate cryptate by single crystal X-ray diffraction reveals that carbonate dianion forms nine complementary hydrogen bonds with the hexacarboxamide cryptand, [CO3鈯?i>mBDCA-5t-H6]2鈥?/sup> (2), a conclusion that is supported by spectroscopic data. Labeling studies and 17O solid-state NMR data confirm that two-thirds of the oxygen atoms in the encapsulated carbonate derive from peroxide dianion, while the carbon is derived from CO. Further evidence for the formation of a carbonate cryptate was obtained by three methods of independent synthesis: treatment of (i) free cryptand with K2CO3; (ii) monodeprotonated cryptand with PPN[HCO3]; and (iii) free cryptand with TBA[OH] and atmospheric CO2. This work demonstrates CO oxidation mediated by a hydrogen-bonding anion receptor, constituting an alternative to transition-metal catalysis.