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Molecules
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Matrix Infrared Spectra and Molecular Structures of Reactive Intermediates
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Matrix Infrared Spectra and Molecular Structures of Reactive Intermediates

A special issue of Molecules (ISSN 1420-3049).

Deadline for manuscript submissions: closed (30 November 2018) | Viewed by 3426

Special Issue Editor

Prof. Dr. Xuefeng Wang

E-Mail Website
Guest Editor
School of Chemical Science and Engineering, Tongji University, Shanghai 200092, China
Interests: metal hydrides; hydrogen bridge bonding; matrix isolation; infrared spectroscopy; computational chemistry; Raman spectroscopy; hydrogen energy chemistry and materials; hydrogen evolution reaction

Special Issue Information

Dear Colleagues,

The reactive intermediates generated in chemical reactions, such as free radicals, unstable ions, and activated complexes, are short-lived and highly reactive. Identification of such chemical species is important to help understand chemical reaction mechanism. The reactive intermediates can be isolated in low temperature matrix, which can be identified by infrared spectroscopy. Such MI-IR (matrix isolation–infrared spectroscopy) technique goes back for many years, which is continuously used to identify the reactive species. The state-of-the-art theoretical calculations are performed to confirm the assignments of matrix infrared spectra and explore reaction mechanism and nature of bonding. This Special Issue will focus on recent progress of matrix isolated reactive intermediates, both experimentally and theoretically.

Prof. Xuefeng Wang
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Reactive intermediates
  • Infrared spectroscopy
  • Matrix isolation
  • Reaction mechanism
  • Computational chemistry
  • Chemical bonding
  • Molecular structure

Published Papers (1 paper)

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Research

16 pages, 2364 KiB  
Article
Chloro- and Dichloro-methylsulfonyl Nitrenes: Spectroscopic Characterization, Photoisomerization, and Thermal Decomposition
by Yang Yang, Xianxu Chu, Yan Lu, Manabu Abe and Xiaoqing Zeng
Molecules 2018, 23(12), 3312; https://doi.org/10.3390/molecules23123312 - 13 Dec 2018
Cited by 4 | Viewed by 3108
Abstract
Chloro- and dichloro-methylsulfonyl nitrenes, CH2ClS(O)2N and CHCl2S(O)2N, have been generated from UV laser photolysis (193 and 266 nm) of the corresponding sulfonyl azides CH2ClS(O)2N3 and CHCl2S(O)2N [...] Read more.
Chloro- and dichloro-methylsulfonyl nitrenes, CH2ClS(O)2N and CHCl2S(O)2N, have been generated from UV laser photolysis (193 and 266 nm) of the corresponding sulfonyl azides CH2ClS(O)2N3 and CHCl2S(O)2N3, respectively. Both nitrenes have been characterized with matrix-isolation IR and EPR spectroscopy in solid N2 (10 K) and glassy toluene (5 K) matrices. Triplet ground-state multiplicity of CH2ClS(O)2N (|D/hc| = 1.57 cm−1 and |E/hc| = 0.0026 cm−1) and CHCl2S(O)2N (|D/hc| = 1.56 cm−1 and |E/hc| = 0.0042 cm−1) has been confirmed. In addition, dichloromethylnitrene CHCl2N (|D/hc| = 1.57 cm−1 and |E/hc| = 0 cm−1), formed from SO2-elimination in CHCl2S(O)2N, has also been identified for the first time. Upon UV light irradiation (365 nm), the two sulfonyl nitrenes R–S(O)2N (R = CH2Cl and CHCl2) undergo concomitant 1,2-R shift to N-sulfonlyamines R–NSO2 and 1,2-oxygen shift to S-nitroso compounds R–S(O)NO, respectively. The identification of these new species with IR spectroscopy is supported by 15N labeling experiments and quantum chemical calculations at the B3LYP/6-311++G(3df,3pd) level. In contrast, the thermally-generated sulfonyl nitrenes CH2ClS(O)2N (600 K) and CHCl2S(O)2N (700 K) dissociate completely in the gas phase, and in both cases, HCN, SO2, HCl, HNSO, and CO form. Additionally, ClCN, OCCl2, HNSO2, •NSO2, and the atmospherically relevant radical •CHCl2 are also identified among the fragmentation products of CHCl2S(O)2N. The underlying mechanisms for the rearrangement and decomposition of CH2ClS(O)2N and CHCl2S(O)2N are discussed based on the experimentally-observed products and the calculated potential energy profile. Full article
(This article belongs to the Special Issue Matrix Infrared Spectra and Molecular Structures of Reactive Intermediates)
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