Brown Timothy A, Hosseini-Nassab Niloufar, Chen Hao, Zare Richard N
Department of Chemistry , Stanford University , Stanford , CA 94305-5080 , USA . Email:
Center for Intelligent Chemical Instrumentation , Department of Chemistry and Biochemistry and Edison Biotechnology Institute , Ohio University , Athens , OH 45701-2979 , USA . Email:
Chem Sci. 2016 Jan 1;7(1):329-332. doi: 10.1039/c5sc02939b. Epub 2015 Oct 8.
We report the observation of the electrochemically generated nitrenium ions of 4,4'-dimethyoxydiphenylamine and di--tolylamine in solution by mass spectrometry. This setup takes inspiration from desorption electrospray ionization mass spectrometry to sample directly from the surface of a rotating waterwheel working electrode for mass spectrometric analysis. Detection of the 4,4'-dimethyoxydiphenylamine nitrenium ion was expected based upon -methoxy resonance stabilization, whereas observation of the di--tolylamine nitrenium ion might be unexpected because resonance stabilization from the -substituted position is unavailable. However, the short timescale analysis of the setup allows for the isolation of the di--tolylamine nitrenium ion, which is electrogenerated in solution and detected mass spectrometrically.
我们报告了通过质谱法在溶液中观察到4,4'-二甲氧基二苯胺和二对甲苯胺的电化学产生的氮鎓离子。此装置的灵感来自解吸电喷雾电离质谱法，可直接从旋转水车工作电极的表面进行采样以进行质谱分析。基于甲氧基共振稳定作用，预计可检测到4,4'-二甲氧基二苯胺氮鎓离子，而二对甲苯胺氮鎓离子的观察结果可能出乎意料，因为来自对位取代位置的共振稳定作用不存在。然而，该装置的短时间尺度分析允许分离在溶液中电生成并通过质谱检测的二对甲苯胺氮鎓离子。
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