Controlling Tautomerization in Pyridine-Fused Phosphorus-Nitrogen Heterocycles

McNeill, J. Nolan; Karas, Lucas J.; Bard, Jeremy P.; Fabrizio, Kevin; Zakharov, Lev N.; MacMillan, Samantha N.; Brozek, Carl K.; Wu, Judy I.; Johnson, Darren W.; Haley, Michael M.

doi:10.1002/chem.202200472

Title: Controlling Tautomerization in Pyridine-Fused Phosphorus-Nitrogen Heterocycles

Journal Article · 25 February 2022 · Chemistry - A European Journal

DOI: https://doi.org/10.1002/chem.202200472 · OSTI ID:1976302

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University of Oregon, Eugene, OR (United States)
University of Houston, TX (United States)
Cornell University, Ithaca, NY (United States)

Abstract Inclusion of a second nitrogen atom in the aromatic core of phosphorus‐nitrogen (PN) heterocycles results in unexpected tautomerization to a nonaromatic form. This tautomerization, initially observed in the solid state through X‐ray crystallography, is also explained by computational analysis. We prepared an electron deficient analogue ( 2 e ) with a fluorine on the pyridine ring and showed that the weakly basic pyridine resisted tautomerization, providing key insights to why the transformation occurs. To study the difference in solution vs. solid‐state heterocycles, alkylated analogues that lock in the quinoidal tautomer were synthesized and their different ¹ H NMR and UV/Vis spectra studied. Ultimately, we determined that all heterocycles are the aromatic tautomer in solution and all but 2 e switch to the quinoidal tautomer in the solid state. Better understanding of this transformation and under what circumstances it occurs suggest future use in a switchable on/off hydrogen‐bond‐directed receptor that can be tuned for complementary hydrogen bonding.

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Research Organization:: Univ. of Oregon, Eugene, OR (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); National Institute of Health; Sloan Research Foundation; USDOE

Grant/Contract Number:: SC0022147; CHE-2107425; CHE-1751370; R35GM133528; FG-2020-12811

OSTI ID:: 1976302

Alternate ID(s):: OSTI ID: 1855305

Journal Information:: Chemistry - A European Journal, Vol. 28, Issue 22; ISSN 0947-6539

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
PN-heterocycles
tautomerization
quinoidal
NICS calculations
x-ray crystallography

CCDC 2118046: Experimental Crystal Structure Determination Nolan, McNeill, J.; J., Karas, Lucas; P., Bard, Jeremy https://doi.org/10.5517/ccdc.csd.cc29302j The current record is supplemented by this dataset	dataset	January 2022
CCDC 2118124: Experimental Crystal Structure Determination Nolan, McNeill, J.; J., Karas, Lucas; P., Bard, Jeremy https://doi.org/10.5517/ccdc.csd.cc2932l3 The current record is supplemented by this dataset	dataset	January 2022
CCDC 2118125: Experimental Crystal Structure Determination Nolan, McNeill, J.; J., Karas, Lucas; P., Bard, Jeremy https://doi.org/10.5517/ccdc.csd.cc2932m4 The current record is supplemented by this dataset	dataset	January 2022
CCDC 2118126: Experimental Crystal Structure Determination Nolan, McNeill, J.; J., Karas, Lucas; P., Bard, Jeremy https://doi.org/10.5517/ccdc.csd.cc2932n5 The current record is supplemented by this dataset	dataset	January 2022

Title: Controlling Tautomerization in Pyridine-Fused Phosphorus-Nitrogen Heterocycles

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References (33)

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Figures / Tables (9)

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