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In our hands these conditions published for the synthesis of meso-boronic acid esters of TAPs by Hyslop et al. did give β-borylated TAPs starting from the respective β-brominated porphyrins, too, but in very low yields e.g, 25-30% for 3a as compared to 70% with our optimized procedure, Table 1, entries 1 and 8
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(a) In our hands these conditions published for the synthesis of meso-boronic acid esters of TAPs by Hyslop et al. did give β-borylated TAPs starting from the respective β-brominated porphyrins, too, but in very low yields (e.g., 25-30% for 3a as compared to 70% with our optimized procedure, Table 1, entries 1 and 8).
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For a recent review on the regioselective borylation of porphyrins by C - H activation, see: (b) Hata, H.; Yamaguchi, S.; Mori, G.; Nakazono, S.; Katoh, T.; Takatsu, K.; Hiroto, S.; Shinokubo, H.; Osuka, A. Cheim. Asian J. 2007, 2, 849-859.
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67849114219
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In the bisporphyrin synthesis by Deng et al.,27 the monomeric coupling partners had no meso substituents, so that no competing intramolecular Heck-like cyclization could occur
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27 the monomeric coupling partners had no meso substituents, so that no competing intramolecular Heck-like cyclization could occur.
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124
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Using KOAc not even traces of the Heck-annulated product 2 were detected by TLC
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Using KOAc not even traces of the Heck-annulated product 2 were detected by TLC.
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For similar results, see: Murata, M.; Watanabe, S.; Masuda, Y. J. Org. Chem. 1997, 62, 6458-6459.
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For the insertion of zinc(II), see: (a) Adler, A. D.; Longo, F. R. J. Inorg. Nucl. Chem. 1970, 32, 2443-2445.
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For the insertion of nickel(II), see: (b) Annoni, E.; Pizzotti, M.; Ugo, R.; Quici, S.; Morotti, T.; Bruschi, M.; Mussini, P. Eur. J. Inorg. Chem. 2005, 3857-3874.
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For the insertion of copper(II), see: (c) Hosseini, A.; Taylor, S.; Accorsi, G.; Armaroli, N.; Reed, C. A.; Boyd, P. D. W. J. Am. Chem. Soc. 2006, 128, 15903-15913.
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For the insertion of copper(II), see: (c) Hosseini, A.; Taylor, S.; Accorsi, G.; Armaroli, N.; Reed, C. A.; Boyd, P. D. W. J. Am. Chem. Soc. 2006, 128, 15903-15913.
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For the insertion of palladium(II), see: (d) Finikova, O. S.; Cheprakov, A. V.; Vinogradov, S. A. J. Org. Chem. 2005, 70, 9562-9572.
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3/MeOH at room temperature resulted in a mixture of bisporphyrins bearing either two nickel(II), two zinc(II), or two different metal centers.
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3/MeOH at room temperature resulted in a mixture of bisporphyrins bearing either two nickel(II), two zinc(II), or two different metal centers.
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For a report on the electronic influence of para substituents on the rotational barriers of the aryl residues in ruthenium, indium, and titanium complexes of meso-tetraarylporphyrins, see: Eaton, S. S.; Eaton, G. R. J. Am. Chetm. Soc. 1977, 99, 6594-6599.
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In agreement with these results, the enantiomeric resolution of previously reported axially chiral meso,meso'-linked bisporphyrins by HPLC on a chiral phase had likewise succeeded only for the fully metalated derivatives.30
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30
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147
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0242515847
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Medforth, C. J, Haddad, R. E, Muzzi, C. M, Dooley, N. R, Jaquinod, L, Shyr, D. C, Nurco, D. J, Olmstead, M. M, Smith, K. M, Ma, J.-G, Shelnutt, J. A. Inorg. Chem. 2003, 42, 2227-2241. For an earlier, yet more special report on phenyl ring rotation in monomeric ruthenium, indium, and titanium tetraarylporphyrins, see ref 55
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Medforth, C. J.; Haddad, R. E.; Muzzi, C. M.; Dooley, N. R.; Jaquinod, L.; Shyr, D. C.; Nurco, D. J.; Olmstead, M. M.; Smith, K. M.; Ma, J.-G.; Shelnutt, J. A. Inorg. Chem. 2003, 42, 2227-2241. For an earlier, yet more special report on phenyl ring rotation in monomeric ruthenium, indium, and titanium tetraarylporphyrins, see ref 55.
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150
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The new dimers described in this paper are configurationally not as stable as the meso,meso'-linked bisporphyrins previously reported.31 The synthesis ofβ,β'-bisporphyrins with additionalβ-substituents next to the central axis is currently in progress in our group
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31 The synthesis ofβ,β'-bisporphyrins with additionalβ-substituents next to the central axis is currently in progress in our group.
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Regarding the rotational barriers the calculations fail to differentiate between the Pd/Pd and the Cu/Cu dimer, certainly because the Pd/Pd complex should be influenced by relativistic effects that can not be taken into account with the used methods
-
Regarding the rotational barriers the calculations fail to differentiate between the Pd/Pd and the Cu/Cu dimer, certainly because the Pd/Pd complex should be influenced by relativistic effects that can not be taken into account with the used methods.
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It is tempting to interpret this potential splitting as being due to different electronic 'communication' between the two porphyrin subunits, also because many other factors like, e.g, ion pairing effects, control the redox splitting significantly.68 On the other hand, Arnold et al. 69 observed an analogous behavior for butadiyne-bridged metalated octaethyl-substituted bis(octaethylporphyrins) and attributed this wave splitting to aggregate formation of cationic porphyrin units.70 Despite the apparent steric hindrance by the meso substituents it might indeed be imaginable that the meso-aryl substituted bisporphyrins in this paper may form aggregates
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70 Despite the apparent steric hindrance by the meso substituents it might indeed be imaginable that the meso-aryl substituted bisporphyrins in this paper may form aggregates.
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