1,2-Diphosphaacenaphthene 1,2-Dications: Synthetic, Stereochemical and Computational Study of the Stabilising Role of Naphthalene-1,8-diyl Backbone

Dhanasekara Mudiyanselage Upulani Kumari Somisara, Michael Buehl, Tomas Lebl, Neville V Richardson, Alexandra Martha Zoya Slawin, J Derek Woollins, Petr Kilian

Research output: Contribution to journalArticlepeer-review

20 Citations (Scopus)

Abstract

Syntheses and full characterisation data (including single crystal diffraction) of three 1,2-diphosphonium dicationic species with the naphthalene-1,8-diyl (Nap) backbone are reported. The oxidation of Nap[(NMe2)(2)](2) with P2I4 to its 1,2-dication was achieved. meso- and rac-forms of "all carbon" 1,2-diphosphonium dications were obtained in good yields and purity by double alkylation of the parent diphosphine (1,2-diphenyl-1,2-diphosphaacenaphthene) with methyl triflate or trimethyloxonium tetrafluoroborate. Each methylating reagent produces one of the rac- or meso-forms of the dication diastereospecifically. Structural parameters of the new dications are discussed with respect to other phosphorus 1,2-dications. DFT (B3LYP) computations revealed the significant role of the naphthalene backbone in stabilisation of the dicationic motif and helped to assess the energy cost of the steric clash of a variety of groups attached to the peri-positions of naphthalene. The synthesis and single crystal X-ray data of the extremely crowded Nap[P(=Se)(OiPr)(2)](2) are discussed, and are contrasted with the unsuccessful synthesis of Nap(PtBu2)(2) from NapLi(2) and ClPtBu2.

Original languageEnglish
Pages (from-to)2666-2677
Number of pages12
JournalChemistry - A European Journal
Volume17
Issue number9
DOIs
Publication statusPublished - 25 Feb 2011

Keywords

  • 1,2-dication
  • organophosphorus
  • peri-substitution
  • organic synthesis
  • POLARIZABLE CONTINUUM MODEL
  • MOLECULAR-STRUCTURES
  • REACTIVITY
  • CHEMISTRY
  • DERIVATIVES
  • COMPOUND
  • DICATION
  • DENSITY
  • SYSTEM

Fingerprint

Dive into the research topics of '1,2-Diphosphaacenaphthene 1,2-Dications: Synthetic, Stereochemical and Computational Study of the Stabilising Role of Naphthalene-1,8-diyl Backbone'. Together they form a unique fingerprint.

Cite this