Nitrile Ylides: Allenic and Propargylic Structures from Pyrazinylnitrenes. Experimental and Theoretical Characterization | Zendy

Didier Bégué | Zendy; Chris Addicott | Zendy; Riko Burgard | Zendy; Paweł Bednarek | Zendy; Émilie Guille | Zendy; Isabelle Baraille | Zendy; Curt Wentrup | Zendy

Open Access

Nitrile Ylides: Allenic and Propargylic Structures from Pyrazinylnitrenes. Experimental and Theoretical Characterization

Author(s) -

Didier Bégué,

Chris Addicott,

Riko Burgard,

Paweł Bednarek,

Émilie Guille,

Isabelle Baraille,

Curt Wentrup

Publication year - 2014

Publication title -

the journal of organic chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.2

H-Index - 228

eISSN - 1520-6904

pISSN - 0022-3263

DOI - 10.1021/jo500002r

Subject(s) - nitrile , chemistry , ylide , anharmonicity , conformational isomerism , molecule , stereochemistry , organic chemistry , physics , quantum mechanics

Matrix photolysis of 2-pyrazinyl azides/tetrazolo[1,5-a]pyrazines generates nitrile ylides 15 via pyrazinylnitrenes 13 and triazacycloheptatetraenes 14. The nitrile ylides 15 are characterized by IR spectroscopy in conjunction with harmonic and anharmonic vibrational frequency calculations. The nitrile ylides exist in the matrices in the Z,Z-conformations in which they are born. Substitution on the nitrile carbon of nitrile ylides has a profound effect on their structure. Even different conformers of the same molecule can have differences up to 200 cm(-1) in the IR absorptions of the ylide moieties. Nitrile ylides 15a and 15b (R = H or Cl, R' = H) have allenic structures (15 Allenic). Nitrile ylide 15c (R = R' = CH3) has a distinctly propargylic structure (15 Propargylic) in the experimentally observed Z,Z-conformation.

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