Research ArticleChemistry

Coordination-induced polymerization of P═C bonds leads to regular (P─C)n polycarbophosphanes

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Science Advances  10 Mar 2021:
Vol. 7, no. 11, eabf4272
DOI: 10.1126/sciadv.abf4272
  • Fig. 1 Polymerization of double bonds.

    (A) Schematic presentation of an addition polymerization of doubly bonded species AB using an initiator I*. (B) Previously used phosphaalkenes for polymerization. (C) Observed microstructure resulting from the polymerization of phosphaalkenes shown in (B).

  • Fig. 2 Synthesis and structures of monomers and their metal complexes.

    (A) Synthesis of 2-phosphanaphthalenes M1 to M3. (B and D) Crystal structures of M3 and 4. (C and E) Synthesis of copper complexes 4 to 6.

  • Fig. 3 NMR spectra and mass analysis by matrix-assisted laser desorption/ionization (MALDI).

    (A) 31P NMR spectra of M2 (top), the reaction mixture of M2 with CuCl in DCM (middle), and the pure P2CuCl (bottom). [The 31P NMR resonance for the PO(OEt)2 group is not significantly affected by complexation or polymerization.] (B) High-mass MALDI-MS spectrum of P2CuCl. m/z, mass/charge ratio.

  • Fig. 4 Synthesis of polymers P2CuCl, P2CuBr, and P3CuCl by coordination-induced polymerization (CIP), their decoordination to give the metalfree polymers P2 and P3, the depolymerization and oxidation.

  • Fig. 5 Proposed simplified mechanism of the polymerization.

    (A) Addition of water to the C═P bond in 4. (B) Possible mechanism for the polymerization of the phosphanaphthalene copper complexes MCuX, represented by M3CuCl. (C) Calculated isotactic pentamer of P3CuCl (left) and P3 (right).

Supplementary Materials

  • Supplementary Materials

    Coordination-induced polymerization of P═C bonds leads to regular (P─C)n polycarbophosphanes

    Yanbo Mei, Juan José Gamboa-Carballo, Yinyin Bao, Na Wu, Grégoire Le Corre, Hansjörg Grützmacher

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    • Supplementary Data
    • Materials, Methods, Experimental Details, and Characterization
    • Tables S1 to S10
    • Figs. S1 to S134
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