Synthetic and structural studies of 1,8-chalcogen naphthalene derivatives

Fergus R. Knight, Amy L. Fuller, Michael Buehl, Alexandra M. Z. Slawin, J. Derek Woollins

Research output: Contribution to journalArticlepeer-review

45 Citations (Scopus)

Abstract

Four novel 1,8-disubstituted naphthalene derivatives 4-7 that contain chalcogen atoms occupying the peri positions have been prepared and fully characterised by using X-ray crystallography, multinuclear NMR spectroscopy, IR spectroscopy and MS. Molecular distortion due to noncovalent substituent interactions was studied as a function of the bulk of the interacting chalcoeen atoms and the size and nature of the alkyl group attached to them. X-ray data for 4-7 was compared to the series of known 1,8-bis-(phenylchalcogeno)naphthalenes 1-3, which were themselves prepared from novel synthetic routes. A general increase in the E center dot center dot center dot E' distance was observed for molecules containing bulkier atoms at the peri positions. The decreased S center dot center dot center dot S distance from phenyl-1 and ethy1-4 analogues is ascribed to a weaker chalcogen lone pair lone pair repulsion acting in the ethyl analogue due to the presence of two equatorial S(naphthyl) ring conformations. Two novel pen-substituted naphthalene sulf-oxides of 1, Nap(O=SPh)(SPh) 8 and Nap(O=SPh), 9, which contain different valence states of sulfur, were prepared and fully characterised by using X-ray crystallography and multinuclear NMR spectroscopy, ER spectroscopy and MS. Molecular structures were analysed by using naphthalene ring torsions, pen-atom displacement, splay angle magnitude, 5 center dot center dot center dot 5 interactions, aromatic ring orientations and quasi-linear O=S center dot center dot center dot S arrangements. The axial S(naphthyl) rings in 8 and 9 are unfavourable for SS contacts due to stronger chalcogen lone pair lone pair repulsion. Although quasi-linear O=S center dot center dot center dot S alignments suggest attractive interaction is conceivable, analysis of the B3LYP wavefunctions affords no evidence for direct bonding interactions between the S atoms.

Original languageEnglish
Pages (from-to)7503-7516
Number of pages14
JournalChemistry - A European Journal
Volume16
Issue number25
Early online date12 May 2010
DOIs
Publication statusPublished - 5 Jul 2010

Keywords

  • ab initio calculations
  • chalcogens
  • density functional calculations
  • naphthalene
  • peri-substitution
  • X-ray diffraction
  • PI-PI STACKING
  • POLYAROMATIC HYDROCARBON LIGANDS
  • RAY-DIFFRACTION DATA
  • X-RAY
  • CRYSTAL-STRUCTURE
  • PERI POSITIONS
  • SUBSTITUTED NAPHTHALENES
  • MOLECULAR-STRUCTURE
  • PLATINUM COMPLEXES
  • LONE-PAIR

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