147-nm photolyses of tetramethylene sulfide, tetramethylene sulfoxide, and tetramethylene sulfone

Journal Article · Thu Nov 26 04:00:00 EST 1981 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j150624a017· OSTI ID:5723533

Scala, A A; Colon, I; Rourke, W

Tetramethylene sulfide, sulfoxide, and sulfone have been photolyzed with 147-nm radiation in the gas and condensed phases. Mechanisms which assume diradical intermediates are presented for the photodecomposition of each compound. The major reaction in all three cases is the elimination of ethylene by a ..beta..-cleavage of the initially formed diradical: XCH/sub 2/CH/sub 2/CH/sub 2/CH/sub 2/. ..-->.. .XCH/sub 2/CH/sub 2/. + C/sub 2/H/sub 4/. The competing ..beta..-cleavage produces X==CH/sub 2/ and C/sub 3/H/sub 6/. This second ..beta..-cleavage is less important in the sulfoxide and the sulfone than it is in the sulfide. The direct elimination of the sulfur atom, and any attached oxygen atoms, is of no importance in the sulfide and of increasing importance as the oxidation state of the sulfur atom increases. The similarity between the mass spectral fragmentation and the vacuum ultraviolet photochemistry of these compounds is noted and the possible involvement of triplet states is mentioned.

• Research Organization: Worcester Polytechnic Inst., MA
• DOE Contract Number: AC02-76ER03569
• OSTI ID: 5723533
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 85:24; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ALKENES
CHALCOGENIDES
CHEMICAL REACTIONS
DATA
DECOMPOSITION
ELECTROMAGNETIC RADIATION
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADIATIONS
SULFIDES
SULFONES
SULFOXIDES
SULFUR COMPOUNDS
ULTRAVIOLET RADIATION