Synthesis of New 9,9′-Spirobifluorene Porphyrins

Abstract

The MacDonald [2+2] type condensation of meso-free dipyrromethane with 9,9′-spirobifluorene aldehyde yields new 5,15-dispiroporphyrins; the large spiro substituents hinder rotation about the meso position to give two atropisomers which can be detected by ¹H NMR after phosphine or isocyanide complexation to the ruthenium spiroporphyrins.

Key words

spiroporphyrins - atropisomers - ruthenium complex - spirobifluorene

References

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19

Spectroscopic Data for Selected Compounds:
DSPH ₂ 1 (α,β and αα): ¹H NMR (CDCl₃/TFA): δ = 10.66 (Hmeso, s, 4 H), 9.26 (H β pyrrole, d, 8 H), 8.74 (H β pyrrole, d, 8 H), 8.45-7.01 (H 9-9′spirobifluorene, m, 60 H). FAB: [M + H]⁺ = 939.3477. UV/VIS (CH₂Cl₂): λ_max/nm (log ε) = 413 (5.41), 507 (4.02), 541 (3.85).
DSPH ₂ 2 (α,β and αα): ¹H NMR (CDCl₃/TFA): δ = 10.07 (Hmeso s, 4 H), 8.4-6.99 (H 9-9′spirobifluorene, m, 60 H), 3.62 (CH₂, m, 16 H), 2.17 (CH₃,s, 12 H), 2.16 (CH₃,s, 12 H), 1.30 (CH₃, td, 12 H), -2.31 (NH, s, 2 H),), -2.32 (NH, s, 2 H). FAB: [M]⁺ = 1107.5353. UV/VIS (CH₂Cl₂): λ_max/nm (log ε) = 408 (5.42), 508 (3.99), 543 (3.85).
(DSP)Ru(CO) 3 (α,β and α,α): ¹H NMR (CDCl₃): δ = 9.95 (Hmeso, s, 4 H), 9.07 (H β pyrrole, d, 8 H), 8.76 (H β pyrrole, d, 8 H), 8.31-6.91 (H 9-9′spirobifluorene, m, 60 H). FAB: [M + H]⁺ = 1067.2349. UV/VIS (CH₂Cl₂): λ_max/nm (log ε) = 404 (5.05), 521 (4.02).
(DSP)Ru(PMePh ₂ ) ₂ 4 (αβ and αα): ¹H NMR (CDCl₃): δ = 9.11 (Hmeso, s, 2 H), 9.06 (Hmeso, s, 2 H), 8.53 (H β pyrrole, d, 4 H), 8.51 (H β pyrrole, d, 4 H), 8.02 (H β pyrrole, d, 4 H), 8.06 (H β pyrrole, d, 4 H), 8.11-6.8 (H 9-9′spirobi-fluorene, m, 60 H), 6.50 (H phosphine p-phenyl ring, t, 4 H), 6.31 (H phosphine p-phenyl ring, m, 4 H), 6.11 (H phosphine m-phenyl ring, m, 16 H), 3.80 (H phosphine o-phenyl ring, m, 4 H), 3.90 (H phosphine o-phenyl ring, m, 8 H), 4.10 (H phosphine o-phenyl ring, m, 4 H), -2.66 (CH₃ phosphine, t, 3 H), -2.76 (CH₃ phosphine, t, 6 H), -2.85 (CH₃ phosphine, t, 3 H). FAB: [M - P(Ph)₂CH₃ + H]⁺ = 1239.46. UV/VIS (CH₂Cl₂): λ_max/nm (log ε) = 426 (5.3), 510 (4).
(DSP)Ru(t-BuCN) ₂ 5 (αβ and αα): ¹H NMR (CDCl₃): δ = 9.46 (Hmeso, s, 4 H), 8,80 (H β pyrrole, d, 8 H), 8.47 (H β pyrrole, m, 8 H), 8.24-6.91 (H 9-9′spirobifluorene, m, 60 H), -0.57 (t-Bu isocyanide, s, 9 H), -0.70 (t-Bu isocyanide, s, 18 H), -0.94 (t-Bu isocyanide, s, 9 H). FAB: [M - t-BuCN + H]⁺ = 1122.36. UV/VIS (CH₂Cl₂): λ_max/nm (log ε) = 411 (5.28), 525 (3.98).
D( o -OMeP)PRu(PMePh ₂ ) ₂ 6: ¹H NMR (CDCl₃): αα: δ = 8.70 (Hmeso, s, 2 H), 8.48 (H β pyrrole, d, 4 H), 8.25 (H β pyrrole, m, 4 H), 7.70-7.41 (H porphyrin phenyl ring, m, 8 H), 6.76 (H phosphine p-phenyl ring, m, 4 H), 6.45 (H phosphine m-phenyl ring, m, 8 H), 4.35 (H phosphine o-phenyl ring, m, 4H), 4.16 (H phosphine o-phenyl ring, m, 4 H), 3.74 (CH₃ methoxy group, s, 6 H), -2.15 (CH₃ phosphine, t, 3 H), -2.37, (CH₃ phosphine, t, 3 H). α,β: δ = 8.68 (Hmeso, s, 2 H), 8.45 (H β pyrrole, d, 4 H), 8.27 (H β pyrrole, m, 4 H), 7.67-7.38 (H porphyrin phenyl ring, m, 8 H), 6.77 (H phosphine p-phenyl ring, t, 4 H), 6.43 (H phosphine m-phenyl ring, t, 8 H), 4.25 (H o-phenyl ring phosphine, m, 8 H), 3.68 (CH₃ methoxy group, s, 6 H), -2.24 (CH₃ phosphine, t, 6 H). FAB: [M - P(Ph)₂CH₃ ]⁺ = 822.1721. UV/VIS (CH₂Cl₂): λ_max/nm (log ε ): 423 (5.13), 507 (3.86).