Fragmentation studies of pentacoordinated bisaminoacylspirophosphoranes by negative electrospray ionization mass spectrometry.
Fragmentation studies of pentacoordinated bisaminoacylspirophosphoranes by negative electrospray ionization mass spectrometry.
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DOI：
10.1002/jms.1900
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发表时间：
2011-03
期刊：
影响因子：
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通讯作者：
S. Cao;Yanchun Guo;Xinshuai Wu;Hua-Rong Zhao;Yufen Zhao
中科院分区：
文献类型：
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作者：
S. Cao;Yanchun Guo;Xinshuai Wu;Hua-Rong Zhao;Yufen Zhao
采用电喷雾多级质谱（ESI-MS（n））负离子模式，研究了一系列五配位双氨酰螺正膦的裂解途径。五配位双氨酰基螺正膦的去质子化离子倾向于消除相应的氨基酸以形成基峰。通过氢/氘交换实验、高分辨质谱、（13）C稳定同位素标记实验和理论计算，对所提出的裂解途径进行了合理化，并验证了裂解途径之间的差异。结果表明，五配位双氨酰螺膦分子的负离子是通过开链的三配位互变异构体解离的。采用B3 LYP/6-31 + + G（d，p）模型计算了产物离子的相对吉布斯自由能（ΔG）和可能的裂解途径.所得结果对螺正膦类化合物的电喷雾质谱（n）鉴定具有一定的应用价值。
Fragmentation pathways of a series of pentacoordinated bisaminoacylspirophosphoranes were elucidated by electrospray ionization multistage mass spectrometry (ESI-MS(n)) in negative mode. The deprotonated ions of pentacoordinated bisaminoacylspirophosphoranes tend to eliminate a corresponding amino acid to form base peak. The hydrogen/deuterium exchange experiment, the high-resolution mass spectrometry, (13)C stable isotope labeling experiment and theoretical calculations were used to rationalize the proposed fragmentation pathways and to verify the differences between the fragmentation pathways. The results indicate that the negative molecular ions of pentacoordinated bisaminoacylspirophosphoranes dissociate through its open-chain tricoordinated tautomers. The relative Gibbs free energies (ΔG) of the product ions and proposed fragmentation pathways were estimated using the B3LYP/6-31 + + G(d, p) model. The results have some potential applications in the identification structures of similar spirophosphorane compounds by ESI-MS(n).