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Synlett 2003(1): 0071-0074
DOI: 10.1055/s-2003-36231
LETTER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of New 9,9′-Spirobifluorene Porphyrins

Cyril Poriel, Yann Ferrand, Paul Le Maux, Gérard Simonneaux*
Laboratoire de Chimie Organométallique et Biologique, UMR CNRS 6509, Université de Rennes 1, 35042 Rennes cedex, France
Fax: +33(2)23235637; e-Mail: gerard.simonneaux@univ-rennes1.fr;
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Publikationsverlauf

Received 30 October 2002
Publikationsdatum:
18. Dezember 2002 (online)

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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

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): λmax/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): λmax/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): λmax/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): λmax/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): λmax/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): λmax/nm (log ε ): 423 (5.13), 507 (3.86).