Compositional Space Boundaries for Organic Compounds

• Published in: Analytical chemistry (Washington) Vol. 84; no. 7; pp. 3410 - 3416
• Main Authors: Lobodin, Vladislav V, Marshall, Alan G, Hsu, Chang Samuel
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 03.04.2012
• Subjects: Analytical chemistry; Carbon; Chemical compounds; Chemistry; Exact sciences and technology; Fossils; Hydrocarbons; Organic chemicals; Molecules; Valence; Fullerene compounds; Hydrocarbon; Hydrogen; Carbon carbon bond; Database; Carbon; Organic compounds; Double bond
• ISSN: 0003-2700; 1520-6882
• DOI: 10.1021/ac300244f

An upper elemental compositional boundary for fossil hydrocarbons has previously been established as double-bond equivalents (i.e., DBE = rings plus double bonds) not exceeding 90% of the number of carbons. For heteroatom-containing fossil compounds, the 90% rule still applies if each N atom is counted as a C atom. The 90% rule eliminates more than 10% of the possible elemental compositions at a given mass for fossil database molecules. However, some synthetic compounds can fall outside the upper boundary defined for naturally occurring compounds. Their inclusion defines an “absolute” upper boundary as DBE (rings plus double bonds to carbon) equal to carbon number plus one, and applies to all organic compounds including fullerenes and other molecules containing no hydrogen. Finally, the DBE definition can fail for molecules with particular atomic valences. Therefore, we also present a generalized DBE definition that includes atomic valence to enable calculation of the correct total number of rings, double bonds, and triple bonds for heteroatom-containing compounds.