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. 2015 Sep 1;4(5):548. doi: 10.1002/open.201500177

Corrigendum: Regioisomer-Free C4h β-Tetrakis(tert-butyl)metallo-phthalocyanines: Regioselective Synthesis and Spectral Investigations

Norihito Iida, Kenta Tanaka, Etsuko Tokunaga, Hiromi Takahashi, Norio Shibata
PMCID: PMC4608518  PMID: 26491630

Due to a calculation error, the charge distribution values are incorrect for the CN groups of 3 b given in Figure 2 a; the corrected figure is shown below. Inline graphic

The corresponding discussion on p. 104 should read: “In order to discuss the high C4h regioselectivity achieved by our methodology, a computation was attempted next. Hanack reported that the regioselectivity of the formation of phthalocyanines depends on the difference in reactivity between two cyano groups of phthalonitrile.[8c] Hence, the charge distributions of two cyano groups on 3 a and 3 b were calculated (DFT/B3LYP/6-31G*) (Figure 2 a). In 3 a, the charge distribution of the cyano group next to the trimethylsilyl group was almost the same as another cyano group (0.269 (C2) versus 0.256 (C1)), which indicates that their reactivity is similar. The charge distribution of each cyano group in 3 b is also almost the same (0.266 (C2) versus 0.245 (C1)). These results are consistent with the experimental observation that the regioselectivity by 3 a and 3 b are the same. Therefore, the regioselectivity of the observed reaction is presumably caused by the steric effect of the trialkylsilyl group (B >>> B’), while the electronic effect is supplemental (A > A’) (Figure 2 b). The steric repulsion between two neighboring trialkylsilyl units on dimer units is the main role for the selectivity. This should be the main reason for the success of the regioselective tetramerization even under very high reaction temperature, while the methodology by Leznoff requires very low reaction temperature due to the reactivity controlled between two cyano groups.[19]

This correction does not influence any of the data presented in the article nor its interpretation. The authors apologize for these mistakes.


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