It has long been known that the photolysis and thermal decomposition of nitrogenous precursors of ethylmethylcarbene would yield different alkene product ratios. However, there exist few mechanistic explanations for such differences. Hence, a complete active space self-consistent field (CASSCF) investigation was conducted with different active spaces to explore the excited-state potential energy surface of the open-shell singlet carbene which is the first excited state of the carbene as a reactive intermediate generated from either the diazirine or diazo precursor. Major emphasis has been explored including the possible birth of the excited state singlet carbene to the multiple hydrogen-migration pathways.  Conical intersections and stationary points were optimized, and they lead to different photoproducts. The effect of different active space has been investigated. Relevant data and results will be presented.

Computational study of the formation and rearrangements of the open–shell excited state of a singlet carbene from diazirine and diazo precursors

244th National Meeting (2012)

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