Improved syntheses of β-octabromo-meso-triarylcorrole derivatives.
In spite of significant applications as starting materials for a variety of metallocorrole derivatives, free-base β-octabromo-meso-triarylcorroles continue to be viewed as inaccessible. The reasons range from the need for tedious column-chromatographic purification to limitations of the reductive demetallation protocol for selected systems. Here we report that column chromatography may be entirely avoided for a number of β-octabromo-meso-tris(p-X-phenyl)corrole derivatives, where X=CF3, NO2, F, H, CH3, and OCH3; instead, analytically pure products may be obtained by recrystallization from chloroform/methanol. In addition, we have presented an optimized synthesis of the heretofore inaccessible, sterically hindered ligand β-octabromo-meso-tris(2,6-dichlorophenyl)corrole, H3[Br8TDCPC], via reductive demetallation of the corresponding Mn(III) complex. With our earlier report of β-octabromo-meso-tris(pentafluorophenyl)corrole, H3[Br8TPFPC], a comprehensive set of optimized synthetic protocols are thus in place for a good number of β-octabromo-meso-triarylcorrole ligands. Furthermore, we have illustrated the use of these ligands by synthesizing the iron complexes Fe[Br8TDCPC]Cl and Fe[Br8TDCPC](py)2, of which the latter lent itself to single-crystal X-ray structure determination.
Department of Chemistry and Center for Theoretical and Computational Chemistry, UiT -The Arctic University of Norway, 9037 Tromsø, Norway.
Jan
J
Capar
Department of Chemistry and Center for Theoretical and Computational Chemistry, UiT -The Arctic University of Norway, 9037 Tromsø, Norway.
Steffen
S
Berg
Department of Chemistry and Center for Theoretical and Computational Chemistry, UiT -The Arctic University of Norway, 9037 Tromsø, Norway.
Kolle E
KE
Thomas
Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720-8229, USA.
Christine M
CM
Beavers
Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720-8229, USA.
Kevin J
KJ
Gagnon
Department of Chemistry and Center for Theoretical and Computational Chemistry, UiT -The Arctic University of Norway, 9037 Tromsø, Norway. Electronic address: abhik.ghosh@uit.no.
Abhik
A
Ghosh
D003300:Copper / Q000737:chemistry; D003460:Crystallization; D007501:Iron / Q000737:chemistry; D008024:Ligands; D008665:Metalloporphyrins / Q000138:chemical synthesis* / Q000737:chemistry; D008968:Molecular Conformation
D008024:Ligands; D008665:Metalloporphyrins; D003300:Copper; D007501:Iron
Corrole; Iron; Metallocorrole; Octabromocorrole; Reductive demetallation