Theoretical Studies on Transannular S⋯S Interactions in Geometrically Constrained 1,5-Dithiocane Derivatives

Richard S Glass, Ludwik Adamowicz, Jeffrey L. Broeker

Research output: Contribution to journalArticle

42 Citations (Scopus)

Abstract

This paper probes, using theoretical calculations, the nature of nonbonded interaction between sulfur functional groups in geometrically constrained 1,5-dithiocane derivatives. Vibronic analysis using SCF/STO-3G* ab initio calculations of the boat conformers of naphtho[1,8-b,c]-l,5-dithiocin (1) and its 1-oxide (2), 1,5-dioxide (3), 1,1-dioxide (4), and 1,1,5-trioxide (5) were carried out. The calculated geometries are close to the experimental geometries determined by single-crystal X-ray crystallographic methods. Comparison of the frequencies of the S⋯S rocking mode for these compounds was used to test whether there is bond formation in 2-5. The results, using this new criterion, show that there is no significant bond formation in 2 and 3 despite the observed geometry changes ascribed to “incipient” bond formation. There is also no attractive interaction in 4 and 5. The weak attraction in 2 and 3 may be due to dipole or charge-transfer interactions.

Original languageEnglish (US)
Pages (from-to)1065-1072
Number of pages8
JournalJournal of the American Chemical Society
Volume113
Issue number4
DOIs
StatePublished - 1991

Fingerprint

Ships
Sulfur
Oxides
Theoretical Models
X-Rays
Derivatives
Geometry
Boats
Functional groups
Charge transfer
Single crystals
X rays

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

@article{486168e74cdb448aaa77add808d9bcaa,
title = "Theoretical Studies on Transannular S⋯S Interactions in Geometrically Constrained 1,5-Dithiocane Derivatives",
abstract = "This paper probes, using theoretical calculations, the nature of nonbonded interaction between sulfur functional groups in geometrically constrained 1,5-dithiocane derivatives. Vibronic analysis using SCF/STO-3G* ab initio calculations of the boat conformers of naphtho[1,8-b,c]-l,5-dithiocin (1) and its 1-oxide (2), 1,5-dioxide (3), 1,1-dioxide (4), and 1,1,5-trioxide (5) were carried out. The calculated geometries are close to the experimental geometries determined by single-crystal X-ray crystallographic methods. Comparison of the frequencies of the S⋯S rocking mode for these compounds was used to test whether there is bond formation in 2-5. The results, using this new criterion, show that there is no significant bond formation in 2 and 3 despite the observed geometry changes ascribed to “incipient” bond formation. There is also no attractive interaction in 4 and 5. The weak attraction in 2 and 3 may be due to dipole or charge-transfer interactions.",
author = "Glass, {Richard S} and Ludwik Adamowicz and Broeker, {Jeffrey L.}",
year = "1991",
doi = "10.1021/ja00004a001",
language = "English (US)",
volume = "113",
pages = "1065--1072",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "4",

}

TY - JOUR

T1 - Theoretical Studies on Transannular S⋯S Interactions in Geometrically Constrained 1,5-Dithiocane Derivatives

AU - Glass, Richard S

AU - Adamowicz, Ludwik

AU - Broeker, Jeffrey L.

PY - 1991

Y1 - 1991

N2 - This paper probes, using theoretical calculations, the nature of nonbonded interaction between sulfur functional groups in geometrically constrained 1,5-dithiocane derivatives. Vibronic analysis using SCF/STO-3G* ab initio calculations of the boat conformers of naphtho[1,8-b,c]-l,5-dithiocin (1) and its 1-oxide (2), 1,5-dioxide (3), 1,1-dioxide (4), and 1,1,5-trioxide (5) were carried out. The calculated geometries are close to the experimental geometries determined by single-crystal X-ray crystallographic methods. Comparison of the frequencies of the S⋯S rocking mode for these compounds was used to test whether there is bond formation in 2-5. The results, using this new criterion, show that there is no significant bond formation in 2 and 3 despite the observed geometry changes ascribed to “incipient” bond formation. There is also no attractive interaction in 4 and 5. The weak attraction in 2 and 3 may be due to dipole or charge-transfer interactions.

AB - This paper probes, using theoretical calculations, the nature of nonbonded interaction between sulfur functional groups in geometrically constrained 1,5-dithiocane derivatives. Vibronic analysis using SCF/STO-3G* ab initio calculations of the boat conformers of naphtho[1,8-b,c]-l,5-dithiocin (1) and its 1-oxide (2), 1,5-dioxide (3), 1,1-dioxide (4), and 1,1,5-trioxide (5) were carried out. The calculated geometries are close to the experimental geometries determined by single-crystal X-ray crystallographic methods. Comparison of the frequencies of the S⋯S rocking mode for these compounds was used to test whether there is bond formation in 2-5. The results, using this new criterion, show that there is no significant bond formation in 2 and 3 despite the observed geometry changes ascribed to “incipient” bond formation. There is also no attractive interaction in 4 and 5. The weak attraction in 2 and 3 may be due to dipole or charge-transfer interactions.

UR - http://www.scopus.com/inward/record.url?scp=0013489374&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0013489374&partnerID=8YFLogxK

U2 - 10.1021/ja00004a001

DO - 10.1021/ja00004a001

M3 - Article

AN - SCOPUS:0013489374

VL - 113

SP - 1065

EP - 1072

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 4

ER -