Boron complexes of porphyrin analogues are rare and typically difficult to prepare. The possibility of extending this chemistry further to include corroles was intriguing and provided the main motivation for this work. The coordination chemistry of boron with corroles was explored. The aim was to see whether boron could be coordinated within the corrole N4 core and if so whether novel or similar structural types resulted, relative to the closely related porphyrin system. Boron halides and aryl halides were reacted with free base corroles in the presence of diisopropylethylamine. The methodology employed was similar to that used for boron porphyrin systems. As well as free base corrole, an N-methyl corrole and trilithiated corrole were also used as starting materials. Several boron corrole structural types were obtained. The reaction of free base corrole with boron trifluoroetherate led to the first structurally characterised corrole with boron bound within the N4 core, B2OF2(corrole). From this reagent a mono-boron species, BF2(corrole) was also obtained. With dichlorophenylborane, several boron corrole complexes were prepared including PhB2O(corrole), PhB2(corrole) and B2Ph2H(corrole). The latter species was structurally characterised and the bridging hydride is proposed to form through a reductive coupling process. Use of N-methyl corrole effectively blocked one boron binding site and subsequently mono-boron corroles BF2(N-methyl- corrole), BPh(OH)(N-methyl corrole) and BPhF(N-methyl corrole) were prepared in good yields. The reaction of lithiated corrole and dichloroplenylborane afforded B2Ph2Cl(corrole). Overall, several new boron corrole species were prepared, significantly extending the library of known boron complexes with ligands related to the porphyrin system.
| Identifer | oai:union.ndltd.org:ADTP/276199 |
| Date | January 2009 |
| Creators | Albrett, Amelia |
| Publisher | ResearchSpace@Auckland |
| Source Sets | Australiasian Digital Theses Program |
| Language | English |
| Detected Language | English |
| Rights | Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated., http://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm, Copyright: The author |
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