Oxidation of Annelated Diarylamines: Analysis of Reaction Pathways to Nitroxide Diradical and Spirocyclic Products
- UNL
Oxidation of diaryldiamine 2, a tetrahydrodiazapentacene derivative, provides diarylnitroxide diradical 1 accompanied by an intermediate nitroxide monoradical and a multitude of isolable diamagnetic products. DFT-computed tensors for EPR spectra and paramagnetic {sup 1}H NMR isotropic shifts for nitroxide diradical 1 show good agreement with the experimental EPR spectra in rigid matrices and paramagnetic {sup 1}H NMR spectra in solution, respectively. Examination of the diamagnetic products elucidates their formation via distinct pathways involving C-O bond-forming reactions, including Baeyer-Villiger-type oxidations. An unusual diiminoketone structure and two spirocyclic structures of the predominant diamagnetic products are confirmed by either X-ray crystallography or correlations between DFT-computed and experimental spectroscopic data such as {sup 1}H, {sup 13}C, and {sup 15}N NMR chemical shifts and electronic absorption spectra.
- Research Organization:
- Advanced Photon Source (APS), Argonne National Laboratory (ANL), Argonne, IL (US)
- Sponsoring Organization:
- NSFAFR
- OSTI ID:
- 1028028
- Journal Information:
- J. Org. Chem., Journal Name: J. Org. Chem. Journal Issue: (20) ; 10, 2011 Vol. 76; ISSN 0022-3263; ISSN JOCEAH
- Country of Publication:
- United States
- Language:
- ENGLISH
Similar Records
Conformationally Constrained, Stable, Triplet Ground State (S = 1) Nitroxide Diradicals. Antiferromagnetic Chains of S = 1 Diradicals
1,3-Alternate calix[4]arene nitronyl nitroxide tetraradical and diradical: synthesis, X-ray crystallography, paramagnetic NMR spectroscopy, EPR spectroscopy, and magnetic studies
Synthesis of Aza-m-Xylylene diradicals with large singlet-triplet energy gap and statistical analyses of their EPR spectra
Journal Article
·
Mon Jun 30 00:00:00 EDT 2008
· J. Am. Chem. Soc.
·
OSTI ID:1007609
1,3-Alternate calix[4]arene nitronyl nitroxide tetraradical and diradical: synthesis, X-ray crystallography, paramagnetic NMR spectroscopy, EPR spectroscopy, and magnetic studies
Journal Article
·
Wed Apr 02 00:00:00 EDT 2008
· Tetrahedron
·
OSTI ID:1007624
Synthesis of Aza-m-Xylylene diradicals with large singlet-triplet energy gap and statistical analyses of their EPR spectra
Journal Article
·
Wed Oct 08 00:00:00 EDT 2014
· Journal of the American Chemical Society
·
OSTI ID:1171258