Non-bonded interactions in 2,2,4,4-tetramethyl-1,3-cyclobutanedithione and 2,2,4,4-tetramethyl-3-thio-1,3-cyclobutanedione

P. K. Basu, U. Chandra Singh, K. N. Tantry, V. Ramamurthy, C. N.R. Rao

Research output: Contribution to journalArticle

8 Scopus citations

Abstract

Electronic absorption and emission spectra as well as He(I) photoelectron spectra of 2,2,4,4-tetramethyl-1,3-cyclobutanedithione and 2,2,4,4-tetramethyl-1-3-thio-1,3-cyclobutanedione have been interpreted on the basis of molecular orbital calculations. The results show that the non-bonded orbital of the dithione is split owing to through-bond interaction, the magnitude of splitting being 0.4 eV. The π* orbital of the dithione appears to be split by about 0.2 eV. Electronic absorption spectra show evidence for the existence of four n-π* transitions, arising out of the splitting of the orbitals referred to above, just as in the case of 2,2,4,4-tetramethyl-1,3-cyclobutanedione. Electronic and photoelectron spectra of the thio-dione show evidence for weak interaction between the CS and C&.zdbnd;O groups, probably via π* orbitals. Infrared spectra of both the dithione and the thio-dione are consistent with the planar cyclobutane ring; the ring-puckering frequency responsible for non-bonded interactions is around 67 cm-1 in both the dithione and the thio-dione, the value not being very different from that in the dione. The 1,3-transannular distance is also similar in the three molecules.

Original languageEnglish (US)
Pages (from-to)237-250
Number of pages14
JournalJournal of Molecular Structure: THEOCHEM
Volume76
Issue number3
DOIs
StatePublished - May 1981
Externally publishedYes

ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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