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

Single-crystal X-ray analysis of the β-heptakis(trifluoromethyl)-meso-tetrakis(p-fluorophenyl)porphyrin, H 2[(CF 3) 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 H 2[(CF 3) 7T pFPP]⋅ 2H 2O and cognate structures may act as supramolecular synthons, which, given their chirality, may even be amenable to resolution into optically pure enantiomers.
Authors:
 [1] ;  [2] ;  [1] ; ORCiD logo [1]
  1. The Arctic University of Norway, Tromso (Norway)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Publication Date:
Grant/Contract Number:
AC02-05CH11231
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
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1436613