Photochemistry of furyl-and thienyldiazomethanes: spectroscopic characterization of triplet 3-thienylcarbene

CR Pharr, LA Kopff, B Bennett, SA Reid…

Index: Pharr, Caroline R.; Kopff, Laura A.; Bennett, Brian; Reid, Scott A.; McMahon, Robert J. Journal of the American Chemical Society, 2012 , vol. 134, # 14 p. 6443 - 6454

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Citation Number: 7

Abstract

Photolysis (λ> 543 nm) of 3-thienyldiazomethane (1), matrix isolated in Ar or N2 at 10 K, yields triplet 3-thienylcarbene (13) and α-thial-methylenecyclopropene (9). Carbene 13 was characterized by IR, UV/vis, and EPR spectroscopy. The conformational isomers of 3- thienylcarbene (sE and sZ) exhibit an unusually large difference in zero-field splitting parameters in the triplet EPR spectrum (| D/hc|= 0.508 cm–1,| E/hc|= 0.0554 cm–1;| D/hc|= ...