TY - JOUR
T1 - Tetrahedral Pegs in Square Holes
T2 - Stereochemistry of Diboron Porphyrazines and Phthalocyanines
AU - Tay, Aaron Chin Yit
AU - Frogley, Benjamin J.
AU - Ware, David C.
AU - Conradie, Jeanet
AU - Ghosh, Abhik
AU - Brothers, Penelope J.
N1 - Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2019/3/4
Y1 - 2019/3/4
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
UR - http://www.scopus.com/inward/record.url?scp=85056829020&partnerID=8YFLogxK
U2 - 10.1002/anie.201810704
DO - 10.1002/anie.201810704
M3 - Article
SN - 1433-7851
VL - 58
SP - 3057
EP - 3061
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 10
ER -