1,2-diphosphaacenaphthene 1,2-dications: synthetic, stereochemical and computational study of the stabilising role of naphthalene-1,8-diyl backbone |
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Authors: | Somisara D M Upulani K Bühl Michael Lebl Tomas Richardson Neville V Slawin Alexandra M Z Woollins J Derek Kilian Petr |
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Institution: | School of Chemistry, EastCHEM, University of St. Andrews, St. Andrews, Fife, UK. |
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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 NapP(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 NapP(?Se)(OiPr)2]2 are discussed, and are contrasted with the unsuccessful synthesis of Nap(PtBu2)2 from NapLi2 and ClPtBu2. |
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Keywords: | 1 2‐dication organophosphorus peri‐substitution organic synthesis |
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