☆ 4.6 Article

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

CHEMISTRY-A EUROPEAN JOURNAL (2011)

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期刊

CHEMISTRY-A EUROPEAN JOURNAL
卷 17, 期 9, 页码 2666-2677

出版社

WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201002259

关键词

1,2-dication; organophosphorus; peri-substitution; organic synthesis

类别

Chemistry, Multidisciplinary

资金

  1. EPSRC
  2. EaStCHEM
  3. Engineering and Physical Sciences Research Council [EP/E010695/1] Funding Source: researchfish
  4. EPSRC [EP/E010695/1] Funding Source: UKRI

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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.

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