http://worldcat.org/entity/work/id/137480733

Reaction Channel Competition in Vibrational Overtone Activation: 1- Methylcyclopropene

Laser vibrational overtone activation has been used to investigate the reaction channel competition in the isomerization of 1 -methylcyclopropene (MCPene). The vibrational overtone activation of three types of CH stretches (methyl, methylenic and olefinic) in the 6vCH transition was initiated and all three products (2-butyne. 1,3-butadiene and 1,2-butadiene) were detected by gas chromatography. Stern-Volmer plots have been constructed for the appearance of each individual product and the derived experimental specific rate coefficients compared to those of RRKM theory. Product ratios of 1,3-butadiene to 2-butyne were independent of pressure. These ratios were compared to the RRKM ratios. The product yield ratio for the methylenic photolysis compared well with the RRKM ratio but the olefinic product yield ratio was approximately 40% lower than the RRKM ratio. The implications of these comparisons are discussed.

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