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13 C CP-MAS NMR studies of S -alkyl-1,4-dithianium salts: conformational motion in the solid state by George W. Wagner; Yu-Chu Yang is a Chemistry article available to read on EtoBox.

What is 13 C CP-MAS NMR studies of S -alkyl-1,4-dithianium salts: conformational motion in the solid state about?

S-(2-chloroethyl)-1,4-dithianium, a persistent solid degradation product of mustard and the major constituent of ''mustard heels'', exhibits motional line-broadening in its 13 C CP-MAS NMR spectrum. Variable temperature examination of the compound and a series of related S-alkyl-1,4-dithianium and thianium salts demonstrates the generality of the motion in these cyclic sulfonium salts. The underlying motional process for the carbons in the six-member rings cannot be attributed to ring rotation, the classical interpretation for cyclohexane, but is consistent with conformational motion. Solid dithiane, and the low temperature phases of cyclohexane and thiane were also studied by variable temperature 13 C MAS NMR to contrast the behavior of these neutral rings with the cyclic sulfonium salts. Distinguishing characteristics of the conformational mechanism include smaller E a 's (2.3-6.1 kcal/mol) and line-broadening (400-600 Hz), compared to the ring-rotation mechanism operative in solid dithiane (12.9 kcal/mol, 1300 Hz) and the low-temperature phase of cyclohexane (11.4 kcal/mol, 925 Hz). The values for the low-temperature phase of thiane (3.8 kcal/mol, 525 Hz) are more consistent wit

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Author

George W. Wagner; Yu-Chu Yang

Publisher

Elsevier Science; Elsevier ; Elsevier BV (ISSN 0022-2860)

Published

1999

Language

EN

Field

Chemistry (Physical Sciences)