Different behavior of nitrenes and carbenes on photolysis and thermolysis: Formation of azirine, ylidic cumulene, and cyclic ketenimine and the rearrangement of 6-phenanthridylcarbene to 9-phenanthrylnitrene

Kvaskoff, David, Bednarek, Pawel, George, Lisa, Pankajakshan, Sreekumar and Wentrup, Curt (2005) Different behavior of nitrenes and carbenes on photolysis and thermolysis: Formation of azirine, ylidic cumulene, and cyclic ketenimine and the rearrangement of 6-phenanthridylcarbene to 9-phenanthrylnitrene. Journal of Organic Chemistry, 70 20: 7947-7955. doi:10.1021/jo050898g


Author Kvaskoff, David
Bednarek, Pawel
George, Lisa
Pankajakshan, Sreekumar
Wentrup, Curt
Title Different behavior of nitrenes and carbenes on photolysis and thermolysis: Formation of azirine, ylidic cumulene, and cyclic ketenimine and the rearrangement of 6-phenanthridylcarbene to 9-phenanthrylnitrene
Journal name Journal of Organic Chemistry   Check publisher's open access policy
ISSN 0022-3263
Publication date 2005-01-01
Sub-type Article (original research)
DOI 10.1021/jo050898g
Volume 70
Issue 20
Start page 7947
End page 7955
Total pages 9
Place of publication United States
Publisher American Chemical Society
Collection year 2005
Language eng
Subject 250303 Physical Organic Chemistry
780103 Chemical sciences
Abstract Flash vacuum thermolysis (FVT) of 9-azidophenanthrene 8, 6-(5-tetrazolyl)phenanthridine 18, and [1,2,3]triazolo[1,5-f]phenanthridine 19 yields 9-cyanofluorene 12 as the principal product and 4-cyanofluorene as a minor product. In all cases, when the product is condensed at or below 77 K, the seven-membered ring ketenimine 24 is detectable by IR spectroscopy (1932 cm(-1)) up to 200 K. Photolysis of Ar matrix isolated 8 at lambda = 308 or 313 nm generates at first the azirine 26, rapidly followed by the ylidic cumulene 27. The latter reverts to azirine 26 at lambda > 405 nm, and the azirine reverts to the ylidic cumulene at 313 nm. Nitrene 9 is observed by ESR spectroscopy following FVT of either azide 8, tetrazole 18, or triazole 19 with Ar matrix isolation of the products. Nitrene 9 and carbene 21 are observed by ESR spectroscopy in the Ar matrix photolyses of azide 8 and triazole 19, respectively.
Keyword Chemistry, Organic
Ab-initio
Excited Molecules
Ring Contraction
Azides
Photochemistry
Phenylnitrenes
Spectroscopy
Expansion
Nitriles
Energies
Q-Index Code C1
Q-Index Status Provisional Code
Additional Notes Erratum: Journal of Organic Chemistry Volume 70, Issue 23, 11 November 2005, Page 9666

 
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Created: Wed, 15 Aug 2007, 15:53:59 EST