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Special Issue "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)

Special Issue Editor

Guest Editor
Prof. Dr. Xuefeng Wang

School of Chemical Science and Engineering, Tongji University, Shanghai 200092, China
Website | E-Mail
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

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Keywords

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

Published Papers (1 paper)

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Research

Open AccessArticle Chloro- and Dichloro-methylsulfonyl Nitrenes: Spectroscopic Characterization, Photoisomerization, and Thermal Decomposition
Molecules 2018, 23(12), 3312; https://doi.org/10.3390/molecules23123312
Received: 27 November 2018 / Revised: 11 December 2018 / Accepted: 12 December 2018 / Published: 13 December 2018
PDF Full-text (2364 KB) | HTML Full-text | XML Full-text | Supplementary Files
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
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