Stabilization and Structure of the cis Tautomer of a Free-Base Porphyrin

Thomas, Kolle E.; McCormick, Laura J.; Vazquez-Lima, Hugo; Ghosh, Abhik

doi:10.1002/anie.201701965

Stabilization and Structure of the cis Tautomer of a Free-Base Porphyrin

Journal Article · Wed Mar 29 04:00:00 EDT 2017 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201701965· OSTI ID:1436613

Thomas, Kolle E. ^[1]; McCormick, Laura J. ^[2]; Vazquez-Lima, Hugo ^[1]; ^[1]

The Arctic University of Norway, Tromso (Norway)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

Single-crystal X-ray analysis of the β-heptakis(trifluoromethyl)-meso-tetrakis(p-fluorophenyl)porphyrin, H₂[(CF₃)₇T_pFPP], 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)₇T_pFPP]∙₂H₂O and cognate structures may act as supramolecular synthons, which, given their chirality, may even be amenable to resolution into optically pure enantiomers.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1436613

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 34 Vol. 56; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Incremental Introduction of Organocatalytic Activity into Conformationally Engineered Porphyrins: Incremental Introduction of Organocatalytic Activity into Conformationally Engineered Porphyrins Kielmann, Marc; Grover, Nitika; Kalisch, Werner W. European Journal of Organic Chemistry, Vol. 2019, Issue 14 https://doi.org/10.1002/ejoc.201801691	journal	February 2019
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Stabilization and Structure of the cis Tautomer of a Free-Base Porphyrin

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