Systematic comparison of the benzynes, pyridynes, and pyridynium cations and characterization of the Bergman cyclization of Z-but-1-en-3-yn-1-y1 isonitrile to the meta diradical 2,4-pyridyne

Stefan L. Debbert, Christopher J. Cramer

Research output: Contribution to journalArticlepeer-review

65 Scopus citations

Abstract

The geometries and relative energies of the singlet and triplet states of the three didehydrobenzenes (benzynes), six didehydropyridines (pyridynes), and six didehydropyridinium (pyridynium) cations are compared at the density functional, multiconfigurational self-consistent field, and coupled cluster levels of theory. The title Bergman cyclization, which produces a meta diradical, is characterized at the density functional theory level and compared to the analogous Bergman cyclizations generating all of the para diradicals in the subject aryne series. Singlet-triplet splittings in the pyridynium cations and 1H hyperfine couplings in the N-protonated pyridyl radicals are found to be well correlated by proportionality constants determined previously for other arynes. Heats of formation (298 K) are predicted for all six pyridynes. (C) 2000 Elsevier Science B.V.

Original languageEnglish (US)
Pages (from-to)1-15
Number of pages15
JournalInternational Journal of Mass Spectrometry
Volume201
Issue number1-3
DOIs
StatePublished - 2000

Bibliographical note

Funding Information:
The authors are grateful for high-performance computing resources, as well as an undergraduate internship, made available by the Minnesota Supercomputer Institute. This work was supported in part by the National Science Foundation, the Alfred P. Sloan Foundation, and the University of Minnesota’s Undergraduate Research Opportunities Program (UROP).

Copyright:
Copyright 2006 Elsevier B.V., All rights reserved.

Keywords

  • Aryne
  • Biradical
  • Didehydroarene
  • Enediyne cyclization
  • Singlet-triplet splitting

Fingerprint

Dive into the research topics of 'Systematic comparison of the benzynes, pyridynes, and pyridynium cations and characterization of the Bergman cyclization of Z-but-1-en-3-yn-1-y1 isonitrile to the meta diradical 2,4-pyridyne'. Together they form a unique fingerprint.

Cite this