Selective Formation of Triplet Alkyl Nitrenes from Photolysis of β-Azido-Propiophenone and Their Reactivity

…, J Sankaranarayanan, S Muthukrishnan…

Index: Singh, Pradeep N. D.; Mandel, Sarah M.; Sankaranarayanan, Jagadis; Muthukrishnan, Sivaramakrishnan; Chang, Mingxin; Robinson, Rachel M.; Lahti, Paul M.; Ault, Bruce S.; Gudmundsdottir, Anna D. Journal of the American Chemical Society, 2007 , vol. 129, # 51 p. 16263 - 16272

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Citation Number: 38

Abstract

Photolysis of β-azido propiophenone derivatives, 1, with built-in sensitizer units, leads to selective formation of triplet alkyl nitrenes 2 that were detected directly with laser flash photolysis (λmax= 325 nm, τ= 27 ms) and ESR spectroscopy (| D/hc|= 1.64 cm-1,| E/hc|= 0.004 cm-1). Nitrenes 2 were further characterized with argon matrix isolation, isotope labeling, and molecular modeling. The triplet alkyl nitrenes are persistent intermediates ...