Tetrahedral Pegs in Square Holes: Stereochemistry of Diboron Porphyrazines and Phthalocyanines

Aaron Chin Yit Tay; Benjamin J. Frogley; David C. Ware; Jeanet Conradie; Abhik Ghosh; Penelope J. Brothers

doi:10.1002/anie.201810704

Tetrahedral Pegs in Square Holes: Stereochemistry of Diboron Porphyrazines and Phthalocyanines

Aaron Chin Yit Tay, Benjamin J. Frogley, David C. Ware, Jeanet Conradie, Abhik Ghosh, Penelope J. Brothers^*

^*Corresponding author for this work

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

11 Citations (Scopus)

Abstract

The first examples of diboron complexes of the tetrapyrroles octaethylporphyrazine (OEPz) and 2,9,16,23-tetra-t-butyl-phthalocyanine (Pc) are reported, counterpoints to the better known monoboron tripyrroles, subporphyrazine and subphthalocyanine. Two stereochemical possibilities are observed, with cisoid-B ₂ OF ₂ (OEPz), both cisoid-B ₂ OPh ₂ (OEPz) and transoid-B ₂ OPh ₂ (OEPz), transoid-B ₂ OF ₂ (Pc) and cisoid-B ₂ OPh ₂ (Pc) having been isolated and characterised, including structure determinations for the OEPz complexes. This variation in stereochemistry, which can be extended to include the previously reported transoid-B ₂ OF ₂ (porphyrin), cisoid-[B ₂ OF ₂ (corrole)] ⁻ , and both transoid- and cisoid-B ₂ OF ₂ (calixphyrin), prompted a wider DFT study to elucidate the factors influencing the stereochemical preferences. This shows that the cisoid/transoid preference is correlated to the ease with which the macrocycle accommodates a rectangularly distorted N ₄ cavity.

Original language	English
Pages (from-to)	3057-3061
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	10
DOIs	https://doi.org/10.1002/anie.201810704
Publication status	Published - 4 Mar 2019

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title = "Tetrahedral Pegs in Square Holes: Stereochemistry of Diboron Porphyrazines and Phthalocyanines",

abstract = " The first examples of diboron complexes of the tetrapyrroles octaethylporphyrazine (OEPz) and 2,9,16,23-tetra-t-butyl-phthalocyanine (Pc) are reported, counterpoints to the better known monoboron tripyrroles, subporphyrazine and subphthalocyanine. Two stereochemical possibilities are observed, with cisoid-B 2 OF 2 (OEPz), both cisoid-B 2 OPh 2 (OEPz) and transoid-B 2 OPh 2 (OEPz), transoid-B 2 OF 2 (Pc) and cisoid-B 2 OPh 2 (Pc) having been isolated and characterised, including structure determinations for the OEPz complexes. This variation in stereochemistry, which can be extended to include the previously reported transoid-B 2 OF 2 (porphyrin), cisoid-[B 2 OF 2 (corrole)] − , and both transoid- and cisoid-B 2 OF 2 (calixphyrin), prompted a wider DFT study to elucidate the factors influencing the stereochemical preferences. This shows that the cisoid/transoid preference is correlated to the ease with which the macrocycle accommodates a rectangularly distorted N 4 cavity.",

keywords = "boron, phthalocyanine, porphyrazine, porphyrin, stereoisomerism",

author = "Tay, \{Aaron Chin Yit\} and Frogley, \{Benjamin J.\} and Ware, \{David C.\} and Jeanet Conradie and Abhik Ghosh and Brothers, \{Penelope J.\}",

note = "Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH \& Co. KGaA, Weinheim",

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AU - Tay, Aaron Chin Yit

AU - Frogley, Benjamin J.

AU - Ware, David C.

AU - Conradie, Jeanet

AU - Ghosh, Abhik

AU - Brothers, Penelope J.

PY - 2019/3/4

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N2 - The first examples of diboron complexes of the tetrapyrroles octaethylporphyrazine (OEPz) and 2,9,16,23-tetra-t-butyl-phthalocyanine (Pc) are reported, counterpoints to the better known monoboron tripyrroles, subporphyrazine and subphthalocyanine. Two stereochemical possibilities are observed, with cisoid-B 2 OF 2 (OEPz), both cisoid-B 2 OPh 2 (OEPz) and transoid-B 2 OPh 2 (OEPz), transoid-B 2 OF 2 (Pc) and cisoid-B 2 OPh 2 (Pc) having been isolated and characterised, including structure determinations for the OEPz complexes. This variation in stereochemistry, which can be extended to include the previously reported transoid-B 2 OF 2 (porphyrin), cisoid-[B 2 OF 2 (corrole)] − , and both transoid- and cisoid-B 2 OF 2 (calixphyrin), prompted a wider DFT study to elucidate the factors influencing the stereochemical preferences. This shows that the cisoid/transoid preference is correlated to the ease with which the macrocycle accommodates a rectangularly distorted N 4 cavity.

AB - The first examples of diboron complexes of the tetrapyrroles octaethylporphyrazine (OEPz) and 2,9,16,23-tetra-t-butyl-phthalocyanine (Pc) are reported, counterpoints to the better known monoboron tripyrroles, subporphyrazine and subphthalocyanine. Two stereochemical possibilities are observed, with cisoid-B 2 OF 2 (OEPz), both cisoid-B 2 OPh 2 (OEPz) and transoid-B 2 OPh 2 (OEPz), transoid-B 2 OF 2 (Pc) and cisoid-B 2 OPh 2 (Pc) having been isolated and characterised, including structure determinations for the OEPz complexes. This variation in stereochemistry, which can be extended to include the previously reported transoid-B 2 OF 2 (porphyrin), cisoid-[B 2 OF 2 (corrole)] − , and both transoid- and cisoid-B 2 OF 2 (calixphyrin), prompted a wider DFT study to elucidate the factors influencing the stereochemical preferences. This shows that the cisoid/transoid preference is correlated to the ease with which the macrocycle accommodates a rectangularly distorted N 4 cavity.

KW - boron

KW - phthalocyanine

KW - porphyrazine

KW - porphyrin

KW - stereoisomerism

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DO - 10.1002/anie.201810704

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ER -

Tetrahedral Pegs in Square Holes: Stereochemistry of Diboron Porphyrazines and Phthalocyanines

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