Sterically crowded peri-substituted naphthalene phosphines and their PV derivatives

Fergus Ross Knight, Amy Fuller, Michael Buehl, Alexandra Martha Zoya Slawin, J Derek Woollins

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Three sterically crowded peri-substituted naphthalene phosphines, Nap[PPh2][ER] (Nap=naphthalene-1,8-diyl; ER=SEt, SPh, SePh) 1–3, which contain phosphorus and chalcogen functional groups at the peri positions have been prepared. Each phosphine reacts to form a complete series of PV chalcogenides Nap[P(E′)(Ph2)(ER)] (E′=O, S, Se). The novel compounds were fully characterised by using X-ray crystallography and multinuclear NMR spectroscopy, IR spectroscopy and MS. X-ray data for 1, 2, nO, nS, nSe (n=1–3) are compared. Eleven molecular structures have been analysed by naphthalene ring torsions, peri-atom displacement, splay angle magnitude, X⋅⋅⋅E interactions, aromatic ring orientations and quasi-linear arrangements. An increase in the congestion of the peri region following the introduction of heavy chalcogen atoms is accompanied by a general increase in naphthalene distortion. P⋅⋅⋅E distances increase for molecules that contain bulkier atoms at the peri positions and also when larger chalcogen atoms are bound to phosphorus. The chalcogenides adopt similar conformations that contain a quasi-linear E⋅⋅⋅PC fragment, except for 3 O, which displays a twist-axial-twist conformation resulting in the formation of a linear O⋅⋅⋅SeC alignment. Ab initio MO calculations performed on 2 O, 3 O, 3 S and 3 Se reveal Wiberg bond index values of 0.02 to 0.04, which indicates only minor non-bonded interactions; however, calculations on radical cations of 3 O, 3 S and 3 Se reveal increased values (0.14–0.19).
Original languageEnglish
Pages (from-to)7617-7634
Number of pages18
JournalChemistry - A European Journal
Issue number25
Publication statusPublished - 5 Jul 2010


  • Chalcogens
  • Density functional calculations
  • Intramolecular interactions
  • Oxidation
  • peri-Substitution
  • X-ray diffraction
  • Polyaromatic hydrocarbon ligands
  • Hexacoordinate silicon-compounds
  • Ray-diffraction data
  • X-ray


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