Ligand Noninnocence in Coinage Metal Corroles: A Silver Knife-Edge.
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.
Department of Chemistry and Center for Theoretical and Computational Chemistry, UiT - The Arctic University of Norway, 9037 Tromsø (Norway).
Kolle E
KE
Thomas
Department of Chemistry and Center for Theoretical and Computational Chemistry, UiT - The Arctic University of Norway, 9037 Tromsø (Norway).
Hugo
H
Vazquez-Lima
Department of Chemistry, University of Houston, Houston, TX 77204-5003 (USA).
Yuanyuan
Y
Fang
Department of Chemistry, University of Houston, Houston, TX 77204-5003 (USA).
Yang
Y
Song
Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720-8229 (USA).
Kevin J
KJ
Gagnon
Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720-8229 (USA).
Christine M
CM
Beavers
Department of Chemistry, University of Houston, Houston, TX 77204-5003 (USA). kkadish@uh.edu.
Karl M
KM
Kadish
Department of Chemistry and Center for Theoretical and Computational Chemistry, UiT - The Arctic University of Norway, 9037 Tromsø (Norway). abhik.ghosh@uit.no.
Abhik
A
Ghosh
coinage metal; copper; gold; noninnocence; silver