Synthesis of (bis)Silicon Complexes of [38], [37], and [36]Octaphyrins: Aromaticity Switch and Stable Radical Cation

Shin Ichiro Ishida; Jinseok Kim; Daiki Shimizu; Dongho Kim; Atsuhiro Osuka

doi:10.1002/anie.201801986

Synthesis of (bis)Silicon Complexes of [38], [37], and [36]Octaphyrins: Aromaticity Switch and Stable Radical Cation

Shin Ichiro Ishida, Jinseok Kim, Daiki Shimizu, Dongho Kim, Atsuhiro Osuka

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

15 Citations (Scopus)

Abstract

Silicon complexation of a [38]octaphyrin (1) was accomplished by reaction with an excess amount of MeSiCl₃ in the presence of N,N-diisopropylethylamine, thus giving an aromatic [38]octaphyrin bis(silicon) complex 2. This complex was interconvertible with an antiaromatic [36]octaphyrin congener (3) by oxidation with MnO₂ and reduction with NaBH₄. Curiously, mild oxidation of 2 with ferrocenium hexafluorophosphate afforded a [37]octaphyrin bis(silicon) complex 4 as an stable radical cation that can be stored under ambient conditions in the solid state. Owing to the two NNNCC-five-coordinated Si atoms bearing trigonal bipyramidal geometry, these octaphyrin bis(silicon) complexes take on similar and rigid figure-of-eight structures with different consecutive numbers of conjugated π-electrons (38, 37, and 36), and are all stable.

Original language	English
Pages (from-to)	5876-5880
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	57
Issue number	20
DOIs	https://doi.org/10.1002/anie.201801986
Publication status	Published - 2018 May 14

Bibliographical note

Funding Information:
The work at Kyoto was supported by JSPS KAKENHI Grant Numbers (Nos.: 25220802 (Scientific Research (S)), 16K13952 (Exploratory Research). The work at Yonsei was supported by the Global Research Laboratory (GRL) Program funded by the Ministry of Science, ICT & Future, Korea (2013K1A1A2A02050183). The authors thank Prof. Dr. N. Aratani at the Nara Institute of Science and Technology (NAIST) for X-ray diffraction analysis and Prof. Dr. T. Ikeue and Mr. Y. Ide at Shimane University for ESR measurement. S.I. and D.S. acknowledge JSPS Fellowship for Young Scientists.

Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)

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10.1002/anie.201801986

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title = "Synthesis of (bis)Silicon Complexes of [38], [37], and [36]Octaphyrins: Aromaticity Switch and Stable Radical Cation",

abstract = "Silicon complexation of a [38]octaphyrin (1) was accomplished by reaction with an excess amount of MeSiCl3 in the presence of N,N-diisopropylethylamine, thus giving an aromatic [38]octaphyrin bis(silicon) complex 2. This complex was interconvertible with an antiaromatic [36]octaphyrin congener (3) by oxidation with MnO2 and reduction with NaBH4. Curiously, mild oxidation of 2 with ferrocenium hexafluorophosphate afforded a [37]octaphyrin bis(silicon) complex 4 as an stable radical cation that can be stored under ambient conditions in the solid state. Owing to the two NNNCC-five-coordinated Si atoms bearing trigonal bipyramidal geometry, these octaphyrin bis(silicon) complexes take on similar and rigid figure-of-eight structures with different consecutive numbers of conjugated π-electrons (38, 37, and 36), and are all stable.",

author = "Ishida, {Shin Ichiro} and Jinseok Kim and Daiki Shimizu and Dongho Kim and Atsuhiro Osuka",

note = "Funding Information: The work at Kyoto was supported by JSPS KAKENHI Grant Numbers (Nos.: 25220802 (Scientific Research (S)), 16K13952 (Exploratory Research). The work at Yonsei was supported by the Global Research Laboratory (GRL) Program funded by the Ministry of Science, ICT & Future, Korea (2013K1A1A2A02050183). The authors thank Prof. Dr. N. Aratani at the Nara Institute of Science and Technology (NAIST) for X-ray diffraction analysis and Prof. Dr. T. Ikeue and Mr. Y. Ide at Shimane University for ESR measurement. S.I. and D.S. acknowledge JSPS Fellowship for Young Scientists. Publisher Copyright: {\textcopyright} 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2018",

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doi = "10.1002/anie.201801986",

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T2 - Aromaticity Switch and Stable Radical Cation

AU - Ishida, Shin Ichiro

AU - Kim, Jinseok

AU - Shimizu, Daiki

AU - Kim, Dongho

AU - Osuka, Atsuhiro

N1 - Funding Information: The work at Kyoto was supported by JSPS KAKENHI Grant Numbers (Nos.: 25220802 (Scientific Research (S)), 16K13952 (Exploratory Research). The work at Yonsei was supported by the Global Research Laboratory (GRL) Program funded by the Ministry of Science, ICT & Future, Korea (2013K1A1A2A02050183). The authors thank Prof. Dr. N. Aratani at the Nara Institute of Science and Technology (NAIST) for X-ray diffraction analysis and Prof. Dr. T. Ikeue and Mr. Y. Ide at Shimane University for ESR measurement. S.I. and D.S. acknowledge JSPS Fellowship for Young Scientists. Publisher Copyright: © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2018/5/14

Y1 - 2018/5/14

N2 - Silicon complexation of a [38]octaphyrin (1) was accomplished by reaction with an excess amount of MeSiCl3 in the presence of N,N-diisopropylethylamine, thus giving an aromatic [38]octaphyrin bis(silicon) complex 2. This complex was interconvertible with an antiaromatic [36]octaphyrin congener (3) by oxidation with MnO2 and reduction with NaBH4. Curiously, mild oxidation of 2 with ferrocenium hexafluorophosphate afforded a [37]octaphyrin bis(silicon) complex 4 as an stable radical cation that can be stored under ambient conditions in the solid state. Owing to the two NNNCC-five-coordinated Si atoms bearing trigonal bipyramidal geometry, these octaphyrin bis(silicon) complexes take on similar and rigid figure-of-eight structures with different consecutive numbers of conjugated π-electrons (38, 37, and 36), and are all stable.

AB - Silicon complexation of a [38]octaphyrin (1) was accomplished by reaction with an excess amount of MeSiCl3 in the presence of N,N-diisopropylethylamine, thus giving an aromatic [38]octaphyrin bis(silicon) complex 2. This complex was interconvertible with an antiaromatic [36]octaphyrin congener (3) by oxidation with MnO2 and reduction with NaBH4. Curiously, mild oxidation of 2 with ferrocenium hexafluorophosphate afforded a [37]octaphyrin bis(silicon) complex 4 as an stable radical cation that can be stored under ambient conditions in the solid state. Owing to the two NNNCC-five-coordinated Si atoms bearing trigonal bipyramidal geometry, these octaphyrin bis(silicon) complexes take on similar and rigid figure-of-eight structures with different consecutive numbers of conjugated π-electrons (38, 37, and 36), and are all stable.

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Synthesis of (bis)Silicon Complexes of [38], [37], and [36]Octaphyrins: Aromaticity Switch and Stable Radical Cation

Abstract

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