Infrared spectroscopic observation of the McLafferty rearrangement in ionized 2-pentanone

Literature Information

Publication Date 2020-08-12
DOI 10.1039/D0CP02602F
Impact Factor 3.676
Authors

Ryo Yasumoto, Yoshiyuki Matsuda, Asuka Fujii


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Abstract

The McLafferty rearrangement is a well-known process in mass spectrometry. In ionization of organic molecules containing a carbonyl group, β cleavage occurs following transfer of a hydrogen atom of aliphatic CH at the γ position to the carbonyl group. Although the McLafferty rearrangement has undergone numerous mass spectrometric investigations, no spectroscopic investigation of the enolized radical cation generated in the hydrogen atom transfer has been carried out. 2-Pentanone is the simplest ketone containing CH bonds at the γ position. In this study, infrared predissociation spectroscopy for both neutral and ionized 2-pentanone in the gas phase through vacuum ultraviolet ionization detection is performed to investigate the ionization-induced isomerization and to observe the enolized product. An OH stretch band is observed in the infrared spectrum of ionized 2-pentanone, and this demonstrates its enolization accompanying the rearrangement of an alkyl hydrogen. The enolization of ionized 2-pentanone is theoretically supported by the reaction path search based on the anharmonic downward distortion following method.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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