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Abstract

Appearance energies for molecular and some fragment ions from 3-methyl-3-acetyl-, 1,2-dimethyl-3-acetyl-, 1,2-dimethyl-3-hydroxycarbonyl- and 1,3-dimethyl-2-(1-methyl)vinylcyclopropenes and model compounds 2,3-dimethylfuran and 1-methylindene were measured by photoionization mass spectrometry. It was shown that, in all cases, the structure of the [M – Me]⁺ ion does not correspond to the expected structures of substituted cyclopropenium ions. Possible schemes for formation of [M – Me]⁺ ions are given. Isodesmic reactions were systematically applied for calculation of the heats of formation for 35 possible C₅H₅O⁺ isomers from 3-methyl-3-acetyl-cyclopropene. In addition, the heats of formation for more than 30 other unsaturated ions and free radicals were estimated with the help of series of isodesmic reactions. A new value of 160 kJ mol⁻¹, as compared with the currently used value of 215.5 kJ mol⁻¹, for the cyclopropylmethyl free radical is suggested. The publication represents the further development of the methodology for the heat of formation estimation procedure for even-electron ions and free radicals.

Keywords

photoionization thermochemistry aromatic ions

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Thermochemistry of Organic and Heteroorganic Species. Part V. Photoionization Studies of Isomerization and Fragmentation of Polysubstituted Cyclopropenes: 3-Methyl-3-Acetyl- and Related Compounds

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