Science Advances

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

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