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1 digital object.

Description

ABSTRACT: An isolable ring-fused pyridinylidene (a so-called Hammick intermediate) was synthesized from a benzo[h]isoquinolinium salt, and its structure in the solid state was determined. The isolation of this first-of-its-kind pyridine-derived aromatic N-heterocyclic carbene was made possible due to the presence of an adamantyl group on nitrogen, forcing the nitrogen to be planar and enhancing both π-donation and steric protection, and to its unique polycyclic structure, which displays an intramolecular C−H···C carbene interaction. Additionally, an example of isomerization of a carbene into another carbene, namely, a benzo[h]isoquinolin-1-ylidene into a benzo[h]isoquinolin-3-ylidene, is reported.

Creation Date

• 2025

Date Issued

• 2025

Authors

• Baslé, Olivier
• Gembicky, Milan
• Gojiashvili, Levan
• Lorkowski, Jan
• Pichon, Delphine
• Roisnel, Thierry
• Talcik, Jakub
• Yorkgitis, Patrick

Principal Investigator

• Bertrand, Guy

Co Principal Investigators

• Jazzar, Rodolphe
• Mauduit, Marc

Funding

This work was supported by the NSF (CHE-2246948) (GB), the “Prematuration Program” of CNRS (MM), the Agence Nationale de la Recherche (ANR) under award #ANR-19-CE07−0017-ChiCAAC (MM, RJ), #ANR-20-CE07−0030-cResolu (MM, RJ), and #ANR-16-CE07−0019 - Hel-NHC (MM, OB).

Topics

• Carbene
• Density functional theory (DFT)
• Domain: Chemical sciences
• Main group
• Organic chemistry
• Pyridine

Format

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• data

Language

• English

Identifier

Identifier: Guy Bertrand: https://orcid.org/0000-0003-2623-2363

Identifier: Jan Lorkowski: https://orcid.org/0000-0003-3436-1296

Identifier: Marc Mauduit: https://orcid.org/0000-0002-7080-9708

Identifier: Milan Gembicky: https://orcid.org/0000-0002-3898-1612

Identifier: Olivier Baslé: https://orcid.org/0000-0002-4551-473X

Identifier: Patrick Yorkgitis: https://orcid.org/0000-0002-5285-0184

Identifier: Rodolphe Jazzar: https://orcid.org/0000-0002-4156-7826

Related Resources

Primary associated publication

• Lorkowski, J; Gojiashvili, L; Yorkgitis, P; Pichon, D; Talcik, J; Gembicky, M; Roisnel, T; Basle, O; Jazzar, R; Mauduit, M; Bertrand, G. A Crystalline Annelated Pyridin-1-ylidene and Its Isomerization into a Pyridin-3-ylidene. J. Am. Chem. Soc. 2025, 147, 18, 14972–14977. https://doi.org/10.1021/jacs.5c05642

Related data

• Jan Lorkowski, Levan Gojiashvili, Patrick Yorkgitis, Delphine Pichon, Jakub Talcik, Milan Gembicky, Thierry Roisnel, Olivier Baslé, Rodolphe Jazzar, Marc Mauduit, Guy Bertrand CCDC 2432544: Experimental Crystal Structure Determination, 2025, https://doi.org/10.5517/ccdc.csd.cc2mn85r
• Jan Lorkowski, Levan Gojiashvili, Patrick Yorkgitis, Delphine Pichon, Jakub Talcik, Milan Gembicky, Thierry Roisnel, Olivier Baslé, Rodolphe Jazzar, Marc Mauduit, Guy Bertrand CCDC 2432545: Experimental Crystal Structure Determination, 2025, https://doi.org/10.5517/ccdc.csd.cc2mn86s
• Jan Lorkowski, Levan Gojiashvili, Patrick Yorkgitis, Delphine Pichon, Jakub Talcik, Milan Gembicky, Thierry Roisnel, Olivier Baslé, Rodolphe Jazzar, Marc Mauduit, Guy Bertrand CCDC 2432546: Experimental Crystal Structure Determination, 2025, https://doi.org/10.5517/ccdc.csd.cc2mn87t
• Jan Lorkowski, Levan Gojiashvili, Patrick Yorkgitis, Delphine Pichon, Jakub Talcik, Milan Gembicky, Thierry Roisnel, Olivier Baslé, Rodolphe Jazzar, Marc Mauduit, Guy Bertrand CCDC 2440123: Experimental Crystal Structure Determination, 2025, https://doi.org/10.5517/ccdc.csd.cc2mx4nc

Collection image

• Image credit: Jan Lorkowski, Patrick Yorkgitis, and Rodolphe Jazzar. "An Isolable and Regioisomerizing Pyridinylidene