Matrix Isolation Spectroscopy Of Reactive Sulfur-containing Species

Reactive sulfur-containing species that play an important role in organic chemistry,materials chemistry and environmental chemistry have always been the research hotspot both in theory and experiment.Their spectra,structure and mechanism have always been the difficulity of physical chemistry,for which they are unstable and easy to rearrange at the room temperature.Due to lack of appropriate synthetic pathway or difficult to capture under conventional conditions,people known little about some long sought sulfur-containing species,such as key radicals involved in the oxidation process of dimethyl sulfide the typical volatile organic sulfur compound and novel sulfur nitrogen multiple-bond isomers tautomerized by nitrene F2P(S)N in its singlet ground state.These sulfur-containing species have important basic research value,especially the spectral detection of the former also has potential applications,which can reveal the reaction channel,provide the standard spectra data for actual air pollution detection and supply theoretical basis for controling and managing the related pollutants.In this paper,we summarized the research progress of key radicals involved in the photooxidation of dimethyl sulfide and reactive sulfur-containing species using nitrene as intermediate.Then we charactrized the radical CH3SO3 and nitrene F2P(S)N by matrix isolation spectroscopy and studied their isomerization processes in conjunction with quantum chemistry calculations.1.Considering the method of producing radicals CF3OSO3 arnd FSO3,we generated the radical CH3SO3,one of the key intermediates in the atmospheric oxidation of dimethyl sulfide,by flash vacuum pyrolysis of precursor CH3S(O)2OOS(O)2CH3 at about 400 ?.This radical was characterized by UV/vis and IR spectroscopy in solid noble gas matrices.Its tautomerization to the carbon-centered radical CH2SO3H and dissociation into CH3O and SO2 were observed upon irradiation.The identification of the result was supported by quantum chemical calculations.2.Upon photolysis(193 nm),the azide F2P(S)N3 generated the nitrene F2P(S)N in its singlet ground state,however,azides are in general explosive.We synthesized the isocyanate F2P(S)NCO having similar properties with azide F2P(S)N3 and stable at room temperature.It was characterized by IR,UV/Vis,Raman and NMR spectroscopy.The vibrational spectra and quantum chemical calculations revealed a single syn conformer existing in the gas and liquid states.Upon an ArF laser(193 rm)photolysis,the isocyanate in solid noble gas matrix yielded the thiophosphoryl nitrene F2P(S)N in the singlet ground state,isomer F2PNS and small molecule F2PNCO.Subsquent photolysis with 365 nm light irradiation caused the formation of another isomer F2PSN and precursor F2P(S)NCO.The IR spectroscopy assignment and structure anslysis of isomers F2P(S)N were supported by quantum chemical calculation.