π-扩展三苯胺和 N-杂三庚烯支架的串联质谱分析:辐射阳离子与银(I)加合物。

IF 1.9 3区 化学 Q3 BIOCHEMICAL RESEARCH METHODS
Marina Kinzelmann, Nina Fröhlich, Alexander Vogel, Milan Kivala, Thomas Drewello
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引用次数: 0

摘要

通过电喷雾离子化(串联)质谱法(ESI-[MS/]MS)研究了具有多达三个低聚苯基延伸的三苯胺(TPA)和 N-杂三庚烯(N-HTA)支架。由于氧化电位较低,所有分子在电喷雾过程中都很容易形成自由基阳离子。分子离子的能量分辨碰撞诱导解离行为与银(I)加合物的能量分辨碰撞诱导解离行为形成对比。与银(I)络合会产生预期的[1:1]和[2:1]络合物(MAg+ 和 M2Ag+);然而,对于具有两个和三个大 π-展开的分子,甚至可以检测到[1:2]络合物(MAg2 2+),从而稳定两个电荷。TPA 支架只有在高碰撞能下才会因外围叔丁基的损失而分解。为此提出了一种一般机制,首先是甲基损失,然后是异丁烯和丁基自由基的释放。基于 N-HTA 的支架的稳定性要差得多,分子离子在低碰撞能量下就会碎裂。这是由于甲基自由基很容易从二甲基亚甲基桥接的三角木核心中流失。与此相反,与 Ag+ 的络合会使其变得非常稳定。最有趣的是,解离最终是通过失去中性的 AgCH3 来进行的,这表明 Ag+ 与分子之间存在强大的双叉镊状键。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Tandem mass spectrometry of π-expanded triphenylamine and N-heterotriangulene scaffolds: Radical cation versus silver(I) adduct

Tandem mass spectrometry of π-expanded triphenylamine and N-heterotriangulene scaffolds: Radical cation versus silver(I) adduct

Triphenylamine (TPA) and N-heterotriangulene (N-HTA) scaffolds with up to three oligophenyl extensions are investigated by electrospray ionization (tandem) mass spectrometry (ESI-[MS/]MS). Due to their low oxidation potentials, all molecules readily form radical cations in the electrospray process. The energy-resolved collision-induced dissociation behaviour of the molecular ions is contrasted to that of the silver(I) adducts. Complexation with Ag(I) leads to the expected [1:1] and [2:1] complexes (MAg+ and M2Ag+); however, even [1:2] complexes (MAg22+) can be detected for molecules with two and three large π-expansions to allow stabilization of two charges. The TPA scaffolds decompose only at high collision energies through the loss of peripheral tert-butyl groups. A general mechanism for this is proposed commencing with a methyl loss and followed by the release of isobutene and butyl radical moieties. The N-HTA-based scaffolds are considerably less stable and molecular ions fragment at low collision energies. This is caused by the facile loss of methyl radicals from the dimethylmethylene-bridged triangulene core. In contrast, complexation with Ag+ leads to a dramatic stabilization. Most interestingly, dissociation eventually proceeds via the loss of neutral AgCH3, which is indicative of strong bidentate, tweezer-like bonding of Ag+ to the molecules.

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来源期刊
Journal of Mass Spectrometry
Journal of Mass Spectrometry 化学-光谱学
CiteScore
5.10
自引率
0.00%
发文量
84
审稿时长
1.5 months
期刊介绍: The Journal of Mass Spectrometry publishes papers on a broad range of topics of interest to scientists working in both fundamental and applied areas involving the study of gaseous ions. The aim of JMS is to serve the scientific community with information provided and arranged to help senior investigators to better stay abreast of new discoveries and studies in their own field, to make them aware of events and developments in associated fields, and to provide students and newcomers the basic tools with which to learn fundamental and applied aspects of mass spectrometry.
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