Spectroscopic Characterization and Catalytic Application of Copper(I), Silver(I) and Gold(I) Carbonyl Cations in Strong Acids
Spectroscopic Characterization and Catalytic Application of Copper(I), Silver(I) and Gold(I) Carbonyl Cations in Strong Acids
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DOI：
10.1246/bcsj.75.2257
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发表时间：
2002-10
影响因子：
4
通讯作者：
Nobuko Tsumori;Qiang Xu;Mai Hirahara;Souichi Tanihata;Y. Souma;Y. Nishimura;N. Kuriyama;S. Tsubota
中科院分区：
文献类型：
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作者：
Nobuko Tsumori;Qiang Xu;Mai Hirahara;Souichi Tanihata;Y. Souma;Y. Nishimura;N. Kuriyama;S. Tsubota
在较宽的温度范围和各种强酸中，对第11族金属羰基阳离子Cu（CO）n+（n = 1，2，3，4），Ag（CO）n+（n = 1，2，3）和Au（CO）n+（n = 1，2）进行了详细的IR，拉曼和NMR光谱表征.在此基础上确定了它们的分子结构，并对它们的稳定性进行了比较和讨论。在浓硫酸中，Cu（CO）2+（Cu（CO）3+为次要活性组分）取代了Cu（CO）3+，Ag（CO）2+取代了Ag（CO）2+，Au（CO）2+取代了Au（CO）2+。先前提出的用于金属羰基阳离子催化的羰基化的反应机理已经被修改为涉及烯烃-金属-单羰基（例如，对于Ag）或烯烃-金属-聚羰基（例如，对于Cu或Au）中间体。
Detailed IR, Raman, and NMR spectroscopic characterization has been carried out on the group 11 metal carbonyl cations, Cu(CO)n+ (n = 1, 2, 3, 4), Ag(CO)n+ (n = 1, 2, 3), and Au(CO)n+ (n = 1, 2), over a wide range of temperature and in a variety of strong acids. Based on these results their molecular structures were determined and their stabilities are compared and discussed. The active species have been determined to be Cu(CO)2+ (and Cu(CO)3+ as a minor species) instead of the previously assigned Cu(CO)3+, Ag(CO)+ instead of the previously assigned Ag(CO)2+, and Au(CO)2+, respectively, for the copper(I), silver(I) and gold(I) carbonyl cation-catalyzed carbonylation of olefins and alcohols in concentrated sulfuric acid. The reaction mechanism previously proposed for the metal carbonyl cation-catalyzed carbonylation has been modified to involve an olefin-metal-monocarbonyl (e.g., for Ag) or an olefin-metal-polycarbonyl (e.g., for Cu or Au) intermediate.