Molecular Structure of Copper and μ-Oxodiiron Octafluorocorrole Derivatives: Insights into Ligand Noninnocence
Abstract
Single-crystal X-ray structures were obtained for the copper and μ-oxodiiron complexes of 2,3,7,8,12,13,17,18-octafluoro-5,10,15-triphenylcorrole, hereafter denoted as Cu[F8TPC] and {Fe[F8TPC]}2O. A comparison with the crystal structures of other undecasubstituted Cu corroles, including those with H, Ar, Br, I, and CF3 as β-substituents, showed that the degree of saddling increases in the order: H ≲ F < Ar ≲ Br ≲ I < CF3. In other words, Cu[F8TPC] is marginally more saddled than β-unsubstituted Cu triarylcorroles, but substantially less saddled than Cu undecaarylcorroles, β-octabromo-meso-triarylcorroles, and β-octaiodo-meso-triarylcorroles, and far less saddled than Cu β-octakis(trifluoromethyl)-meso-triarylcorroles. As for {Fe[F8TPC]}2O, the moderate quality of the structure did not allow us to draw firm conclusions in regard to bond length alternations in the corrole skeleton and hence also the question of ligand noninnocence. The Fe-O bond distances, 1.712(8) and 1.724(8), however, are essentially identical to those observed for {Fe[TPFPC]}2O, where TPFPC3- is the trianion of 5,10,15-tris(pentafluorophenyl)corrole, suggesting that a partially noninnocent electronic structural description may be applicable for both compounds.
- Authors:
-
[2];
[1]
- The Arctic University of Norway (UiT), Tromsø (Norway)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS); Univ. of California, Berkeley, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Research Council of Norway
- OSTI Identifier:
- 1760240
- Grant/Contract Number:
- AC02-05CH11231; 262229
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Omega
- Additional Journal Information:
- Journal Volume: 5; Journal Issue: 17; Journal ID: ISSN 2470-1343
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Thomas, Kolle E., Settineri, Nicholas S., Teat, Simon J., Steene, Erik, and Ghosh, Abhik. Molecular Structure of Copper and μ-Oxodiiron Octafluorocorrole Derivatives: Insights into Ligand Noninnocence. United States: N. p., 2020.
Web. doi:10.1021/acsomega.0c01035.
Thomas, Kolle E., Settineri, Nicholas S., Teat, Simon J., Steene, Erik, & Ghosh, Abhik. Molecular Structure of Copper and μ-Oxodiiron Octafluorocorrole Derivatives: Insights into Ligand Noninnocence. United States. https://doi.org/10.1021/acsomega.0c01035
Thomas, Kolle E., Settineri, Nicholas S., Teat, Simon J., Steene, Erik, and Ghosh, Abhik. Thu .
"Molecular Structure of Copper and μ-Oxodiiron Octafluorocorrole Derivatives: Insights into Ligand Noninnocence". United States. https://doi.org/10.1021/acsomega.0c01035. https://www.osti.gov/servlets/purl/1760240.
@article{osti_1760240,
title = {Molecular Structure of Copper and μ-Oxodiiron Octafluorocorrole Derivatives: Insights into Ligand Noninnocence},
author = {Thomas, Kolle E. and Settineri, Nicholas S. and Teat, Simon J. and Steene, Erik and Ghosh, Abhik},
abstractNote = {Single-crystal X-ray structures were obtained for the copper and μ-oxodiiron complexes of 2,3,7,8,12,13,17,18-octafluoro-5,10,15-triphenylcorrole, hereafter denoted as Cu[F8TPC] and {Fe[F8TPC]}2O. A comparison with the crystal structures of other undecasubstituted Cu corroles, including those with H, Ar, Br, I, and CF3 as β-substituents, showed that the degree of saddling increases in the order: H ≲ F < Ar ≲ Br ≲ I < CF3. In other words, Cu[F8TPC] is marginally more saddled than β-unsubstituted Cu triarylcorroles, but substantially less saddled than Cu undecaarylcorroles, β-octabromo-meso-triarylcorroles, and β-octaiodo-meso-triarylcorroles, and far less saddled than Cu β-octakis(trifluoromethyl)-meso-triarylcorroles. As for {Fe[F8TPC]}2O, the moderate quality of the structure did not allow us to draw firm conclusions in regard to bond length alternations in the corrole skeleton and hence also the question of ligand noninnocence. The Fe-O bond distances, 1.712(8) and 1.724(8), however, are essentially identical to those observed for {Fe[TPFPC]}2O, where TPFPC3- is the trianion of 5,10,15-tris(pentafluorophenyl)corrole, suggesting that a partially noninnocent electronic structural description may be applicable for both compounds.},
doi = {10.1021/acsomega.0c01035},
journal = {ACS Omega},
number = 17,
volume = 5,
place = {United States},
year = {Thu Apr 23 00:00:00 EDT 2020},
month = {Thu Apr 23 00:00:00 EDT 2020}
}
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