Research ArticleChemistry

Constraint of a ruthenium-carbon triple bond to a five-membered ring

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Science Advances  22 Jun 2018:
Vol. 4, no. 6, eaat0336
DOI: 10.1126/sciadv.aat0336
  • Fig. 1 Development of transition metal carbyne complexes.

    L, ligand.

  • Fig. 2 The synthesis, structure, and aromaticity of ruthenapentalynes 2.

    (A) Synthesis of ruthenapentalynes 2 from carbolongs 1. DCM, dichloromethane. (B) X-ray molecular structure for the cation of ruthenapentalyne 2a (the ellipsoids are drawn at the 50% probability level; phenyl groups and ester groups are omitted for clarity; the detailed structure is presented in fig. S1). (C) ASE evaluation of the aromaticity of ruthenapentalyne 2a. (D) Nucleus-independent chemical shift (NICS)(1)zz evaluations of aromaticity of model complex 2a′. (E) AICD plot of model complex 2a′ with an isosurface value of 0.03. The magnetic field vector is orthogonal to the ring plane and points upward (aromatic species exhibit clockwise diatropic circulations).

  • Fig. 3 Ambiphilic reactivity and [2 + 2] cycloaddition reaction of ruthenapentalynes.

    (A) Reactions of 2 with sodium thiophenoxide and CuCl, Cl2CHCOOH, and CF3COOD. (B) The proposed mechanism for the metal-carbon triple bond shift reaction of ruthenapentalyne 2b in the presence of acid. (C) X-ray crystal structures of the cations of 3b, 4a, and 6 (the ellipsoids are drawn at the 50% probability level; phenyl groups of 3b, 4a, and 6 and ester groups of 4a are omitted for clarity; the detailed structures are presented in figs. S2 to S4 for 3b, 4a, and 6, respectively).

  • Fig. 4 Cascade cyclization reactions of ruthenapentalyne 2a.

    (A) Cascade cyclization reactions of 2a with ambident nucleophiles. (B) X-ray molecular structures for complexes 7 and 8 (the ellipsoids are drawn at the 50% probability level; phenyl groups and ester groups are omitted for clarity; the detailed structures are presented in figs. S5 and S6 for 7 and 8, respectively). (C) Proposed mechanism for the formation of 7.

  • Fig. 5 UV-vis absorption spectra of 2a, 3a, 4a, 6, 7, and 8.

    Measured in CH2Cl2 at RT (1.0 × 10−4 M).

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/4/6/eaat0336/DC1

    fig. S1. X-ray molecular structure for the cation of complex 2a.

    fig. S2. X-ray molecular structure for the cation of complex 3b.

    fig. S3. X-ray molecular structure for the cation of complex 4a.

    fig. S4. X-ray molecular structure for the cation of complex 6.

    fig. S5. X-ray molecular structure for complex 7.

    fig. S6. X-ray molecular structure for complex 8.

    fig. S7. Gibbs free-energy pathway for the DFT-calculated formation mechanism of complex 2a at 298 K.

    fig. S8. A plausible mechanism for the formation of complex 8.

    fig. S9. ASE evaluation of complex 3b.

    fig. S10. NICS evaluations of model complex 3b′.

    fig. S11. AICD plot of the model complex 3b′ with an isosurface value of 0.03.

    fig. S12. AICD plot of the model complex 2a′ with an isosurface value of 0.03.

    fig. S13. Resonance structures of complexes 4.

    fig. S14. Positive-ion ESI-MS spectrum of [2a]+ [C68H57ClO4P3Ru]+ measured in methanol.

    fig. S15. Positive-ion ESI-MS spectrum of [2b]+ [C63H51ClOP3Ru]+ measured in methanol.

    fig. S16. Positive-ion ESI-MS spectrum of [3a]+ [C75H62O5P3RuS]+ measured in methanol.

    fig. S17. Positive-ion ESI-MS spectrum of [3b]+ [C70H56O2P3RuS]+ measured in methanol.

    fig. S18. Positive-ion ESI-MS spectrum of [4a]+ [C68H57Cl2CuO4P3Ru]+ measured in methanol.

    fig. S19. Positive-ion ESI-MS spectrum of [4b]+ [C63H51Cl2CuOP3Ru]+ measured in methanol.

    fig. S20. Positive-ion ESI-MS spectrum of [5]+ [C63H51OClP3Ru]+ measured in dichloromethane.

    fig. S21. Positive-ion ESI-MS spectrum of [5′]+ [C63H50DOClP3Ru]+ measured in dichloromethane.

    fig. S22. Positive-ion ESI-MS spectrum of [6]+ [C67H57ClO2P3Ru]+ measured in methanol.

    fig. S23. Positive-ion ESI-MS spectrum of [7 + H]+ [C70H58N2O6P3Ru]+ measured in methanol.

    fig. S24. Positive-ion ESI-MS spectrum of [8 + H]+ [C72H58N6O4P3Ru]+ measured in methanol.

    fig. S25. 1H NMR spectrum (600.1 MHz) of complex 2a in CD2Cl2 at RT.

    fig. S26. 31P NMR spectrum (242.9 MHz) of complex 2a in CD2Cl2 at RT.

    fig. S27. 13C NMR spectrum (150.9 MHz) of complex 2a in CD2Cl2 at RT.

    fig. S28. 1H NMR spectrum (300.1 MHz) of complex 2b in CD2Cl2/CD3OD (v/v = 3/1) at RT.

    fig. S29. 31P NMR spectrum (121.5 MHz) of complex 2b in CD2Cl2/CD3OD (v/v = 3/1) at RT.

    fig. S30. 13C NMR spectrum (75.5 MHz) of complex 2b in CD2Cl2/CD3OD (v/v = 3/1) at RT.

    fig. S31. 1H NMR spectrum (500.2 MHz, CD2Cl2) of complex 3a at RT.

    fig. S32. 31P NMR spectrum (202.5 MHz, CD2Cl2) of complex 3a at RT.

    fig. S33. 13C NMR spectrum (125.8 MHz, CD2Cl2) of complex 3a at RT.

    fig. S34. 1H NMR spectrum (300.1 MHz, CD2Cl2) of complex 3b at RT.

    fig. S35. 31P NMR spectrum (121.5 MHz, CD2Cl2) of complex 3b at RT.

    fig. S36. 13C NMR spectrum (75.5 MHz, CD2Cl2) of complex 3b at RT.

    fig. S37. 1H NMR spectrum (400.1 MHz, CD2Cl2) of complex 4a at RT.

    fig. S38. 31P NMR spectrum (161.9 MHz, CD2Cl2) of complex 4a at RT.

    fig. S39. 13C NMR spectrum (100.6 MHz, CD2Cl2) of complex 4a at RT.

    fig. S40. 1H NMR spectrum (600.1 MHz, CD2Cl2) of complex 4b at RT.

    fig. S41. 31P NMR spectrum (242.9 MHz, CD2Cl2) of complex 4b at RT.

    fig. S42. 13C NMR spectrum (150.5 MHz, CD2Cl2) of complex 4b at RT.

    fig. S43. In situ 1H NMR spectrum (600.1 MHz, CD2Cl2) of complex 5 at 0°C.

    fig. S44. In situ 31P NMR spectrum (242.9 MHz, CD2Cl2) of complex 5 at 0°C.

    fig. S45. In situ 13C NMR spectrum (150.9 MHz, CD2Cl2) of complex 5 at 0°C.

    fig. S46. In situ 1H NMR spectrum (500.2 MHz, CD2Cl2/CH3COOD = 10/1) of complex 5′ at 0°C.

    fig. S47. In situ 31P NMR spectrum (202.5 MHz, CD2Cl2/CH3COOD = 10/1) of complex 5′ at 0°C.

    fig. S48. 1H NMR spectrum (300.1 MHz, CD2Cl2) of complex 6 at RT.

    fig. S49. 31P NMR spectrum (121.5 MHz, CD2Cl2) of complex 6 at RT.

    fig. S50. 13C NMR spectrum (75.5 MHz, CD2Cl2) of complex 6 at RT.

    fig. S51. 1H NMR spectrum (600.1 MHz, CD2Cl2) of complex 7 at RT.

    fig. S52. 31P NMR spectrum (242.9 MHz, CD2Cl2) of complex 7 at RT.

    fig. S53. 13C NMR spectrum (150.9 MHz, CD2Cl2) of complex 7 at RT.

    fig. S54. 1H NMR spectrum (400.1 MHz, CDCl3) of complex 8 at RT.

    fig. S55. 31P NMR spectrum (161.9 MHz, CDCl3) of complex 8 at RT.

    table S1. Crystal data and structure refinement for 2a, 3b, and 4a.

    table S2. Crystal data and structure refinement for 6, 7, and 8.

    table S3. Response to the questions raised in the checkCIF reports of complexes 4a, 7, and 8.

    table S4. Thermal decomposition data of complexes 2 to 4 and 6 to 8 in the solid state.

    Supplementary Materials and Methods

    data file S1. CIF files for complexes 2a, 3b, 4a, 6, 7, and 8.

    data file S2. Cartesian coordinate–optimized structures for ASE, NICS, and AICD calculations.

    data file S3. Cartesian coordinate–optimized structures for mechanism studies.

    References (5260)

  • Supplementary Materials

    This PDF file includes:

    • fig. S1. X-ray molecular structure for the cation of complex 2a.
    • fig. S2. X-ray molecular structure for the cation of complex 3b.
    • fig. S3. X-ray molecular structure for the cation of complex 4a.
    • fig. S4. X-ray molecular structure for the cation of complex 6.
    • fig. S5. X-ray molecular structure for complex 7.
    • fig. S6. X-ray molecular structure for complex 8.
    • fig. S7. Gibbs free-energy pathway for the DFT-calculated formation mechanism of complex 2a at 298 K.
    • fig. S8. A plausible mechanism for the formation of complex 8.
    • fig. S9. ASE evaluation of complex 3b.
    • fig. S10. NICS evaluations of model complex 3b′.
    • fig. S11. AICD plot of the model complex 3b′ with an isosurface value of 0.03.
    • fig. S12. AICD plot of the model complex 2a′ with an isosurface value of 0.03.
    • fig. S13. Resonance structures of complexes 4.
    • fig. S14. Positive-ion ESI-MS spectrum of 2a+ C68H57ClO4P3Ru+ measured in methanol.
    • fig. S15. Positive-ion ESI-MS spectrum of2b+ C63H51ClOP3Ru+ measured in methanol.
    • fig. S16. Positive-ion ESI-MS spectrum of 3a+ C75H62O5P3RuS+ measured in methanol.
    • fig. S17. Positive-ion ESI-MS spectrum of 3b+ C70H56O2P3RuS+ measured in methanol.
    • fig. S18. Positive-ion ESI-MS spectrum of 4a+ C68H57Cl2CuO4P3Ru+ measured in methanol.
    • fig. S19. Positive-ion ESI-MS spectrum of 4b+ C63H51Cl2CuOP3Ru+ measured in methanol.
    • fig. S20. Positive-ion ESI-MS spectrum of 5+ C63H51OClP3Ru+ measured in dichloromethane.
    • fig. S21. Positive-ion ESI-MS spectrum of 5+ C63H50DOClP3Ru+ measured in dichloromethane.
    • fig. S22. Positive-ion ESI-MS spectrum of 6+ C67H57ClO2P3Ru+ measured in methanol.
    • fig. S23. Positive-ion ESI-MS spectrum of 7 + H+ C70H58N2O6P3Ru+ measured in methanol.
    • fig. S24. Positive-ion ESI-MS spectrum of 8 + H+ C72H58N6O4P3Ru+ measured in methanol.
    • fig. S25. 1H NMR spectrum (600.1 MHz) of complex 2a in CD2Cl2 at RT.
    • fig. S26. 31P NMR spectrum (242.9 MHz) of complex 2a in CD2Cl2 at RT.
    • fig. S27. 13C NMR spectrum (150.9 MHz) of complex 2a in CD2Cl2 at RT.
    • fig. S28. 1H NMR spectrum (300.1 MHz) of complex 2b in CD2Cl2/CD3OD (v/v = 3/1) at RT.
    • fig. S29. 31P NMR spectrum (121.5 MHz) of complex 2b in CD2Cl2/CD3OD (v/v = 3/1) at RT.
    • fig. S30. 13C NMR spectrum (75.5 MHz) of complex 2b in CD2Cl2/CD3OD (v/v = 3/1) at RT.
    • fig. S31. 1H NMR spectrum (500.2 MHz, CD2Cl2) of complex 3a at RT.
    • fig. S32. 31P NMR spectrum (202.5 MHz, CD2Cl2) of complex 3a at RT.
    • fig. S33. 13C NMR spectrum (125.8 MHz, CD2Cl2) of complex 3a at RT.
    • fig. S34. 1H NMR spectrum (300.1 MHz, CD2Cl2) of complex 3b at RT.
    • fig. S35. 31P NMR spectrum (121.5 MHz, CD2Cl2) of complex 3b at RT.
    • fig. S36. 13C NMR spectrum (75.5 MHz, CD2Cl2) of complex 3b at RT.
    • fig. S37. 1H NMR spectrum (400.1 MHz, CD2Cl2) of complex 4a at RT.
    • fig. S38. 31P NMR spectrum (161.9 MHz, CD2Cl2) of complex 4a at RT.
    • fig. S39. 13C NMR spectrum (100.6 MHz, CD2Cl2) of complex 4a at RT.
    • fig. S40. 1H NMR spectrum (600.1 MHz, CD2Cl2) of complex 4b at RT.
    • fig. S41. 31P NMR spectrum (242.9 MHz, CD2Cl2) of complex 4b at RT.
    • fig. S42. 13C NMR spectrum (150.5 MHz, CD2Cl2) of complex 4b at RT.
    • fig. S43. In situ 1H NMR spectrum (600.1 MHz, CD2Cl2) of complex 5 at 0°C.
    • fig. S44. In situ 31P NMR spectrum (242.9 MHz, CD2Cl2) of complex 5 at 0°C.
    • fig. S45. In situ 13C NMR spectrum (150.9 MHz, CD2Cl2) of complex 5 at 0°C.
    • fig. S46. In situ 1H NMR spectrum (500.2 MHz, CD2Cl2/CH3COOD = 10/1) of complex 5′ at 0°C.
    • fig. S47. In situ 31P NMR spectrum (202.5 MHz, CD2Cl2/CH3COOD = 10/1) of complex 5′ at 0°C.
    • fig. S48. 1H NMR spectrum (300.1 MHz, CD2Cl2) of complex 6 at RT.
    • fig. S49. 31P NMR spectrum (121.5 MHz, CD2Cl2) of complex 6 at RT.
    • fig. S50. 13C NMR spectrum (75.5 MHz, CD2Cl2) of complex 6 at RT.
    • fig. S51. 1H NMR spectrum (600.1 MHz, CD2Cl2) of complex 7 at RT.
    • fig. S52. 31P NMR spectrum (242.9 MHz, CD2Cl2) of complex 7 at RT.
    • fig. S53. 13C NMR spectrum (150.9 MHz, CD2Cl2) of complex 7 at RT.
    • fig. S54. 1H NMR spectrum (400.1 MHz, CDCl3) of complex 8 at RT.
    • fig. S55. 31P NMR spectrum (161.9 MHz, CDCl3) of complex 8 at RT.
    • table S1. Crystal data and structure refinement for 2a, 3b, and 4a.
    • table S2. Crystal data and structure refinement for 6, 7, and 8.
    • table S3. Response to the questions raised in the checkCIF reports of complexes 4a, 7, and 8.
    • table S4. Thermal decomposition data of complexes 2 to 4 and 6 to 8 in the solid state.
    • Supplementary Materials and Methods
    • References (52–60)

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    Other Supplementary Material for this manuscript includes the following:

    • data file S1 (.cif format). CIF files for complexes 2a, 3b, 4a, 6, 7, and 8.
    • data file S2 (.xyz format). Cartesian coordinate–optimized structures for ASE, NICS, and AICD calculations.
    • data file S3 (.xyz format). Cartesian coordinate–optimized structures for mechanism studies.

    Download Data files S1 to S3

    Files in this Data Supplement:

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