Mechanistic Studies of Photochemical Reactions with Millisecond Time Resolution by Electrospray Ionization Mass Spectrometry

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• 作者：Wei Ding ; Keith A. Johnson ; Charles Kutal ; and I. Jonathan Amster
• 刊名：Analytical Chemistry
• 出版年：2003
• 出版时间：September 1, 2003
• 年：2003
• 卷：75
• 期：17
• 页码：4624 - 4630
• 全文大小：131K
• 年卷期：v.75,no.17(September 1, 2003)
• ISSN：1520-6882

文摘

Electrospray ionization mass spectrometry is used asan on-line technique to investigate the solution photochemistry of [CpFebz]⁺ (Cp, images/gifchars/eta.gif" BORDER=0 >⁵-cyclopentadienyl; bz,images/gifchars/eta.gif" BORDER=0 >⁶-benzene). Direct irradiation of samples in the opticallytransparent tip of the electrospray source allows thedetection of products with lifetimes down to the millisecond regime. Photolysis of [CpFebz]⁺ in acetonitrile(AN) yields the short-lived half-sandwich complex, [CpFe(AN)₃]⁺. The suspected parent-offspring relationshipbetween this species and the fully ring-deligated product,[Fe(AN)₆]²⁺, has been confirmed. In solutions containingcyclohexene oxide, [CpFebz]⁺ generates several photoproducts capable of initiating the cationic polymerizationof the epoxide monomer. The initiation process and thefirst few steps in the subsequent growth of the polymerchain have been observed.