Probing Cyanocuprates by Electrospray Ionization Mass Spectrometry
Probing Cyanocuprates by Electrospray Ionization Mass Spectrometry
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通过电喷雾电离质谱法探测氰基铜酸盐
DOI：
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发表时间：
2010
期刊：
影响因子：
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通讯作者：
K. Koszinowski
中科院分区：
文献类型：
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作者：
Aliaksei Putau;K. Koszinowski
通过电喷雾电离质谱法分析CuCN/（RLi）n（n = 0.5、0.8、1.0和2.0，R = Me、Et、nBu、sBu、tBu和Ph）的四氢呋喃溶液。在所有情况下，观察到有机铜酸盐阴离子，其确切性质取决于试剂的化学计量。在CuCN/（RLi）2溶液中，不含氰化物的Lin− 1CunR 2n −阴离子占绝对优势，而在n ≤ 1的CuCN/（RLi）n试剂中，含氰化物的Lin−1CunRn（CN）n−络合物占优势。混合研究与CuCN/MeLi/RLi以及气相碎裂实验的质量选择的阴离子提供了进一步的了解的相对稳定性和可能的结构组成的多核铜酸盐。由此获得的信息不仅同意相当不错，与以前的结果从光谱学和晶体学的工作，而且揭示了明确的趋势，不同的有机取代基如何影响聚集和离子配对行为的cyanocuprates。此外，还对含Cu（+2）的氰基铜酸盐配合物的结构进行了研究。
Solutions of CuCN/(RLi)n (n = 0.5, 0.8, 1.0, and 2.0 and R = Me, Et, nBu, sBu, tBu, and Ph) in tetrahydrofuran are analyzed by electrospray ionization mass spectrometry. In all cases, organocuprate anions are observed, whose exact nature depends on the reagent stoichiometry. While cyanide-free Lin−1CunR2n− anions completely predominate for CuCN/(RLi)2 solutions, cyanide-containing Lin−1CunRn(CN)n− complexes prevail for CuCN/(RLi)n reagents with n ≤ 1. Mixing studies with CuCN/MeLi/RLi as well as gas-phase fragmentation experiments of the mass-selected anions provide further insight into the relative stability and the likely structural composition of polynuclear cuprates. The thus obtained information not only agrees quite well with previous results from spectroscopic and crystallographic work but moreover reveals clear trends of how different organyl substituents influence the aggregation and ion-pairing behavior of cyanocuprates. In addition, the observation of Cu(+2)-containing cyanocuprate complexes fo...