Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 21, Issue 47, Pages 16839-16847Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201502150
Keywords
coinage metal; copper; gold; noninnocence; silver
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Funding
- FRINATEK of the Research Council of Norway [163054, 231086]
- Robert A. Welch Foundation [E-680]
- Advanced Light Source, Berkeley, California
- Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy [DE-AC02-05CH11231]
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A silver beta-octabromo-meso-triarylcorrole has been found to exhibit a strongly saddled geometry, providing the first instance of a strongly saddled corrole complex involving a metal other than copper. The Soret maxima of the Ag octabromocorroles also redshift markedly in response to increasingly electron-donating para substituents on the mesoaryl groups. In both these respects, the Ag octabromocorroles differ from simple Ag triarylcorrole derivatives, which exhibit only mild saddling and substituent-insensitive Soret maxima. These results have been rationalized in terms of an innocent M-III-corrole(3-) description for the simple Ag corroles and a noninnocent M-II-corrole(center dot 2-) description for the Ag octabromocorroles. In contrast, all copper corroles are thought to be noninnocent, while all gold corroles are innocent. Uniquely among metallocorroles, silver corroles thus seem poised on a knife-edge, so to speak, between innocent and noninnocent electronic structures and may tip either way, depending on the exact nature of the corrole ligand.
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