Tetrahedral Pegs in Square Holes: Stereochemistry of Diboron Porphyrazines and Phthalocyanines. Issue 10 (20th November 2018)

• Record Type: Journal Article
• Authors: Tay, Aaron Chin Yit; Frogley, Benjamin J.; Ware, David C.; Conradie, Jeanet; Ghosh, Abhik; Brothers, Penelope J.
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 10(2019)
• Page Start: 3057
• Page End: 3061
• Publication Date: 2018-11-20
• Subjects: boron -- phthalocyanine -- porphyrazine -- porphyrin -- stereoisomerism; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201810704
• Languages: English
• ISSNs: 1433-7851

Abstract

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 ‐B2 OF2 (OEPz), both cisoid ‐B2 OPh2 (OEPz) and transoid ‐B2 OPh2 (OEPz), transoid ‐B2 OF2 (Pc) and cisoid ‐B2 OPh2 (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 ‐B2 OF2 (porphyrin), cisoid ‐[B2 OF2 (corrole)] −, and both transoid ‐ and cisoid ‐B2 OF2 (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 N4 cavity. Abstract : Fully characterised boron complexes of porphyrazine and phthalocyanine contain FBOBF and PhBOBPh moieties in both cisoid and transoid geometries. A DFT study, extended to include the previously reported FBOBF porphyrin, corrole, and calixphyrin complexes shows that the stereochemical preferences correlate with the ease with which each macrocycle can accommodate a rectangularly distorted N4 cavity.