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The hypothiocyanite radical OSCN and its isomers
Zhuang Wu1, Jian Xu, Qifan Liu
1College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 215123 Suzhou, P. R. China. xqzeng@suda.edu.cn.
Physical Chemistry Chemical Physics : PCCP
|June 17, 2017
Summary
Researchers generated the reactive sulfur species hypothiocyanite radical (OSCN) and its novel isomers. Light irradiation induced reversible isomerization between these species, identified using spectroscopy and computational chemistry.
Area of Science:
- Chemical Physics
- Spectroscopy
- Computational Chemistry
Background:
- Reactive sulfur species (RSS) play crucial roles in biological systems.
- The hypothiocyanite radical (OSCN) is a biologically relevant RSS.
- Understanding the structure and reactivity of RSS is vital for biological and chemical research.
Purpose of the Study:
- To generate and characterize the hypothiocyanite radical (OSCN) in the gas phase.
- To investigate the photoisomerization of OSCN to novel isomers OSNC and SOCN.
- To explore the potential energy surface and bonding properties of OSCN isomers.
Main Methods:
- Flash vacuum pyrolysis (FVP) of trifluoromethyl sulfinyl cyanide (CF3S(O)CN) at ~1000 K to generate OSCN.
- UV (365 nm) and visible (400 ± 20 nm) light irradiation to induce and reverse isomerization.
- Identification of isomers in cryogenic matrices (Ar, N2 at 2.8 K) using IR spectroscopy.
- Quantum chemical calculations (CCSD(T)-F12/VTZ-F12, EDA-NOCV) to support experimental findings and explore potential energy surfaces.
Main Results:
- Successful generation of the hypothiocyanite radical (OSCN) via FVP.
- Observation of light-induced reversible isomerization between OSCN, OSNC, and SOCN.
- Experimental identification of OSCN, OSNC, and SOCN isomers supported by high-level computational chemistry.
- Detailed computational analysis of the potential energy surface and bonding characteristics of the interconverting isomers.
Conclusions:
- The study successfully synthesized and characterized novel isomers of the hypothiocyanite radical (OSCN).
- Photoisomerization provides a pathway for interconverting these reactive sulfur species.
- Computational methods confirm the structures and bonding of the observed isomers, advancing the understanding of reactive sulfur chemistry.
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