Stabilization and Structure of the cis Tautomer of a Free-Base Porphyrin
Abstract
Single-crystal X-ray analysis of the β-heptakis(trifluoromethyl)-meso-tetrakis(p-fluorophenyl)porphyrin, H2[(CF3)7TpFPP], has revealed the first example of a stable cis tautomer of a free-base porphyrin, the long-postulated intermediate of porphyrin tautomerism. The stability of the unique molecule appears to reflect a dual origin: a strongly saddled porphyrin skeleton, which alleviates electrostatic repulsion between the two NH protons, and two polarization-enhanced, transannular N-H∙∙∙O-H∙∙∙N hydrogen bond chains, each involving a molecule of water. DFT calculations suggest that the observed tautomer has a lower energy than the alternative, doubly hydrated trans tautomer by some 8.3 kcal mol-1 . A fascinating prospect thus exists that H2[(CF3)7TpFPP]∙2H2O and cognate structures may act as supramolecular synthons, which, given their chirality, may even be amenable to resolution into optically pure enantiomers.
- Authors:
-
[1]
- The Arctic University of Norway, Tromso (Norway)
- 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)
- OSTI Identifier:
- 1436613
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 34; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Thomas, Kolle E., McCormick, Laura J., Vazquez-Lima, Hugo, and Ghosh, Abhik. Stabilization and Structure of the cis Tautomer of a Free-Base Porphyrin. United States: N. p., 2017.
Web. doi:10.1002/anie.201701965.
Thomas, Kolle E., McCormick, Laura J., Vazquez-Lima, Hugo, & Ghosh, Abhik. Stabilization and Structure of the cis Tautomer of a Free-Base Porphyrin. United States. https://doi.org/10.1002/anie.201701965
Thomas, Kolle E., McCormick, Laura J., Vazquez-Lima, Hugo, and Ghosh, Abhik. Wed .
"Stabilization and Structure of the cis Tautomer of a Free-Base Porphyrin". United States. https://doi.org/10.1002/anie.201701965. https://www.osti.gov/servlets/purl/1436613.
@article{osti_1436613,
title = {Stabilization and Structure of the cis Tautomer of a Free-Base Porphyrin},
author = {Thomas, Kolle E. and McCormick, Laura J. and Vazquez-Lima, Hugo and Ghosh, Abhik},
abstractNote = {Single-crystal X-ray analysis of the β-heptakis(trifluoromethyl)-meso-tetrakis(p-fluorophenyl)porphyrin, H2[(CF3)7TpFPP], has revealed the first example of a stable cis tautomer of a free-base porphyrin, the long-postulated intermediate of porphyrin tautomerism. The stability of the unique molecule appears to reflect a dual origin: a strongly saddled porphyrin skeleton, which alleviates electrostatic repulsion between the two NH protons, and two polarization-enhanced, transannular N-H∙∙∙O-H∙∙∙N hydrogen bond chains, each involving a molecule of water. DFT calculations suggest that the observed tautomer has a lower energy than the alternative, doubly hydrated trans tautomer by some 8.3 kcal mol-1 . A fascinating prospect thus exists that H2[(CF3)7TpFPP]∙2H2O and cognate structures may act as supramolecular synthons, which, given their chirality, may even be amenable to resolution into optically pure enantiomers.},
doi = {10.1002/anie.201701965},
journal = {Angewandte Chemie (International Edition)},
number = 34,
volume = 56,
place = {United States},
year = {2017},
month = {3}
}
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Figures / Tables:
Figure 1: Thermal ellipsoid plots (33%) of H2[(CF3)7TpFPP]·2H2O: (a) top view and (b) close-up of the porphyrin core with hydrogen bond distances (Å).
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