Ligand Noninnocence in Coinage Metal Corroles: A Silver Knife-Edge.

Autor: Thomas KE; Department of Chemistry and Center for Theoretical and Computational Chemistry, UiT - The Arctic University of Norway, 9037 Tromsø (Norway)., Vazquez-Lima H; Department of Chemistry and Center for Theoretical and Computational Chemistry, UiT - The Arctic University of Norway, 9037 Tromsø (Norway)., Fang Y; Department of Chemistry, University of Houston, Houston, TX 77204-5003 (USA)., Song Y; Department of Chemistry, University of Houston, Houston, TX 77204-5003 (USA)., Gagnon KJ; Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720-8229 (USA)., Beavers CM; Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720-8229 (USA)., Kadish KM; Department of Chemistry, University of Houston, Houston, TX 77204-5003 (USA). kkadish@uh.edu., Ghosh A; Department of Chemistry and Center for Theoretical and Computational Chemistry, UiT - The Arctic University of Norway, 9037 Tromsø (Norway). abhik.ghosh@uit.no.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2015 Nov 16; Vol. 21 (47), pp. 16839-47. Date of Electronic Publication: 2015 Sep 08.
DOI: 10.1002/chem.201502150
Abstrakt: A silver β-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 meso-aryl 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(·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.
(© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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