Supporting Information

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1 Supporting Information Reply to Comment on Estimated Gas-Phase Standard State Enthalpies of Formation for Organic Compounds Using the Gaussian-4 (G4) and W1BD Theoretical Methods Sierra Rayne*, and Kaya Forest Ecologica Research, Kelowna, British Columbia, Canada V1Y 1R9; Department of Chemistry, Okanagan College, Penticton, British Columbia, Canada V2A 8E1 * Corresponding author. rayne.sierra@gmail.com. Ecologica Research. Okanagan College. S1

2 Example articles employing various atomization energy/enthalpy approaches: Ball, D. W. Nitrohydrazines as potential high energy materials: High level calculations. J. Mol. Struct. (Theochem) 2006, 773, 1-7. Bond, D. Computational methods in organic thermochemistry. 1. Hydrocarbon enthalpies and free energies of formation. J. Org. Chem. 2007, 72, Chen, C. Theoretical study of synthetic reaction of tetrazole and tetrazolate anion. Int. J. Quant. Chem. 2000, 80, Csaszar, A. G.; Leininger, M. L.; Burcat, A. Enthalpy of formation of 2Π3/2 SH. J. Phys. Chem. A 2003, 107, Cundari, T. R.; Leza, H. A. R.; Grimes, T.; Steyl, G.; Waters, A.; Wilson, A. K. Calculation of the enthalpies of formation for transition metal complexes. Chem. Phys. Lett. 2005, 401, da Silva, G.; Bozzelli, J. W.; Sebbar, N.; Bockhorn, H. Thermodynamic and ab initio analysis of the controversial enthalpy of formation of formaldehyde. ChemPhysChem 2006, 7, Dixon, D. A.; Feller, D.; Christe, K. O.; Wilson, W. W.; Vij, A.; Vij, V.; Jenkins, H. D. B.; Olson, R. M.; Gordon, M. S. Enthalpies of formation of gas-phase N3, N3-, N5+, and N5- from ab initio molecular orbital theory, stability predictions for N5+N3and N5+N5-, and experimental evidence for the instability of N5+N3-. J. Am. Chem. Soc. 2004, 126, Fabian, W. M. F. Accurate thermochemistry from quantum chemical calculations? Monatsh. Chem. 2008, 139, Glukhovtsev, M. N.; Laiter, S. High level ab initio stabilization energies of benzene. Theor. Chim. Acta 1995, 92, Gomes, J. R. B.; da Silva, M. A. V. R. Thermochemistry of small organosulfur compounds from ab initio calculations. J. Phys. Chem. A 2004, 108, Harding, M. E.; Gauss, J.; Pfluger, K.; Werner, H. J. High-accuracy extrapolated ab initio thermochemistry of vinyl chloride. J. Phys. Chem. A 2007, 111, Haworth, N. L.; Smith, M. H.; Bacskay, G. B.; Mackie, J. C. Heats of formation of hydrofluorocarbons obtained by Gaussian-3 and related quantum chemical computations. J. Phys. Chem. A 2000, 104, Kieninger, M.; Ventura, O. N. Computational determination of the enthalpy of formation of alkylthial S-oxides and alkylthione S-oxides: A study of (Z)propanethial-S-oxide, the lachrymatory factor of the onion (Allium cepa). Phys. Chem. Chem. Phys. 2002, 4, Kiselev, V. G.; Gritsan, N. P.; Zarko, V. E.; Kalmykov, P. I.; Shandakov, V. A. Multilevel quantum chemical calculation of the enthalpy of formation of [1,2,5]oxadiazolo[3,4-e][1,2,3,4]-tetrazine-4,6-di-N-dioxide. Comb. Explos. Shock Waves 2007, 43, Klopper, W.; Noga, J. Accurate quantum-chemical prediction of enthalpies of formation of small molecules in the gas phase. ChemPhysChem 2003, 4, S2

3 Kormos, B. L.; Liebman, J. F.; Cramer, C. J. 298 K enthalpies of formation of monofluorinated alkanes: Theoretical predictions for methyl, ethyl, isopropyl and tert-butyl fluoride. J. Phys. Org. Chem. 2004, 17, Lazarou, Y. G.; Prosmitis, A. V.; Papadimitriou, V. C.; Papagiannakopoulous, P. Theoretical calculation of bond dissociation energies and enthalpies of formation for halogenated molecules. J. Phys. Chem. A 2001, 105, Li, H. X.; Zhang, R. Z.; Yang, X. D.; Zhang, H. Density functional studies of the heats of formation of several nitroester compounds. J. Mol. Struct. (Theochem) 2007, 815, Liu, M. H.; Chen, C.; Liu, C. W.; Hong, Y. S. Theoretical study on thermodynamic properties of C1-C16 alkanes: A 3-parameter least-squared calibration. J. Phys. Chem. A 2004, 108, Matulis, V. E.; Ivashkevich, O. A.; Gaponik, P. N.; Elkind, P. D.; Sukhanov, G. T.; Bazyleva, A. B.; Zaitsau, D. H. Theoretical study of gas-phase formation enthalpies and isomerism for 4(5)-nitro-1,2,3-triazole and its N-alkyl derivatives and experimental determination of formation enthalpy for 2-methyl-4-nitro-1,2,3triazole. J. Mol. Struct. (Theochem) 2008, 854, Mo, O.; Yanez, M.; Elguero, J.; Roux, M. V.; Jimenez, P.; Davalos, J. Z.; da Silva, M. A. V. R.; da Silva, M. D. D. M. C. R.; Cabildo, P.; Claramunt, R. Substituent effects on enthalpies of formation: Benzene derivatives. J. Phys. Chem. A 2003, 107, Notario, R.; Castano, O.; Gomperts, R.; Frutos, L. M.; Palmeiro, R. Organic thermochemistry at high ab initio levels. 3. A G3 study of cyclic saturated and unsaturated hydrocarbons (including aromatics). J. Org. Chem. 2000, 65, Novak, I.; Pratt, L. M. Computational study of lithioprismanes. Chem. Phys. Lett. 400, 2004, Parthiban, S.; Martin, J. M. L. Assessment of W1 and W2 theories for the computation of electron affinities, ionization potentials, heats of formation, and proton affinities. J. Chem. Phys. 2001, 114, Poutsma, J. C.; Schroeder, O. E.; Squires, R. R. Experimental chloride ion affinities and theoretical predictions for the absolute heats of formation of SiCl2 and SiClF. Chem. Phys. Lett. 2004, 389, Sabbe, M. K.; Saeys, M.; Reyniers, M. F.; Marin, G. B.; van Speybroeck, V.; Waroquier, M. Group additive values for the gas phase standard enthalpy of formation of hydrocarbons and hydrocarbon radicals. J. Phys. Chem. A 2005, 109, Sicre, J. E.; Cobos, C. J. Thermochemistry of the higher chlorine oxides ClOx (x=3,4) and Cl2Ox (x=3-7). J. Mol. Struct. (Theochem) 2003, 620, Simmie, J. M.; Black, G.; Curran, H. J.; Hinde, J. P. Enthalpies of formation and bond dissociation energies of lower alkyl hydroperoxides and related hydroperoxy and alkoxy radicals. J. Phys. Chem. A 2008, 112, Su, X.; Cheng, X.; Liu, Y.; Li, Q. Theoretical calculation of bond dissociation energies and heats of formation for nitromethane and polynitromethanes with density functional theory. Int. J. Quant. Chem. 2007, 107, S3

4 Tasi, G.; Izsak, R.; Matisz, G.; Csaszar, A. G.; Kallay, M.; Ruscic, B.; Stanton, J. F. The origin of systematic error in the standard enthalpies of formation of hydrocarbons computed via atomization schemes. ChemPhysChem 2006, 7, Ventura, O. N.; Kieninger, M.; Denis, P. A. Density functional computational thermochemistry: Determination of the enthalpy of formation of methanethial-s,sdioxide (sulfene). J. Phys. Chem. A 2003, 107, Wang, L.; Heard, D. E.; Pilling, M. J.; Seakins, P. A Gaussian-3X prediction on the enthalpies of formation of chlorinated phenols and dibenzo-p-dioxins. J. Phys. Chem. A 2008, 112, Wei, T.; Zhang, J.; Zhu, W.; Zhang, X.; Xiao, H. A comparison of high-level theoretical methods to predict the heats of formation of azo compounds. J. Mol. Struct. (Theochem) 2010, 956, Wu, J.; Xu, X. The X1 method for accurate and efficient prediction of heats of formation. J. Chem. Phys. 2007, 127, S4

5 Table S1. Gas phase total energies at 0 K and enthalpies at K for all compounds from ref. [1] at the G4 level of theory. compound chlorotrifluoromethane cyanogen chloride difluorodichloromethane phosgene fluorotrichloromethane tetrachloromethane carbonic difluoride tetrafluoromethane trichloromethane trifluoromethane hydrogen cyanide dichloromethane difluoromethane formaldehyde formic acid chloromethane methane methanol methanethiol methylamine carbon monoxide carbon dioxide carbon disulfide chlorotrifluoroethene tetrachloroethene trifluoroacetonitrile tetrafluoroethene trichloroethene trifluoroethene acetylene 1,1-dichloroethene cis-1,2-dichloroethene trans-1,2-dichloroethene 1,1-difluoroethene chloroethene 1,1,1-trichloroethane fluoroethene 1,1,1-trifluoroethane acetonitrile ethylene acetaldehyde ethylene oxide acetic acid ethane ethanol dimethyl sulfoxide dimethylamine propyne cyclopropene propene cyclopropane acetone oxetane S5 E H

6 propylene oxide trimethylamine pyrazine pyrimidine pyridazine furan diketene thiophene pyrrole cyclopropanecarbonitrile cyclobutene methylenecyclopropane 1-methylcyclopropene bicyclo[1.1.0]butane cis-2-butene trans-2-butene 2-methyl-1-propene tetrahydrofuran butane isobutane pyridine bicyclo[1.1.0]butane-1-carbonitrile 1,3-cyclopentadiene 2-methyl-1-buten-3-yne cyclopropylacetylene bicyclo[2.1.0]pent-2-ene spiropentane bicyclo[2.1.0]pentane 1,1-dimethylcyclopropane pentane isopentane neopentane benzene fulvene 3,4-dimethylenecyclobut-1-ene tris(methylene)cyclopropane phenol aniline 2-methylpyridine bicyclo[2.1.0]pentane-1-carbonitrile hexane 2,2-dimethylbutane 2,3-dimethylbutane toluene 2,5-norbornadiene quadricyclane spiro[2,4]hepta-4,6-diene anti-tricyclo[ ,4]hept-6-ene tetracyclo[ ,4.03,5]heptane 1,2-bis(methylene)cyclobutane 3-methylenecyclopentene bicyclo[2.1.1]hex-2-ene bicyclo[2.2.0]hex-1(4)-ene benzyne phenylacetylene bicyclo[4.2.0]octa-1,3,5-triene 3,6-bis(methylene)-1,4-cyclohexadiene S

7 1-cyclopropylpenta-1,3-diyne cyclopropylbenzenea trans-bicyclo[6.1.0]nona-2,4,6-triene cis-bicyclo[4.3.0]nona-3,7-diene octahydrodicyclopropa[cd,gh]pentalene (1α,2α,4α,5α)-tricyclo[ ,4]oct-6-ene bicyclo[3.2.1]octa-2,6-diene 2,3-bis(methylene)bicyclo[2.2.0]hexane 7-methylenebicyclo[2.2.1]heptane anti-tricyclo[ ,5]octane 1-propynylbenzene hexafluorobenzene 1,2,3-trichlorobenzene 1,2,4-trichlorobenzene 1,3,5-trichlorobenzene o-dichlorobenzene m-dichlorobenzene p-dichlorobenzene o-difluorobenzene m-difluorobenzene p-difluorobenzene chlorobenzene 1-buten-3-yne bicyclo[1.1.0]but-1(3)-ene (Z)-3-penten-1-yne (Z)-hexa-1,5-diyne-3-ene (E)-hexa-1,5-diyne-3-ene 1,2-bis(methylene)cyclobutane trans-2,3,4-hexatriene cis-2,3,4-hexatriene bicyclo[2.2.0]hexane 1,1-diethynylcyclopropane bicyclo[3.2.0]hepta-2,6-diene 3-methylene-1,4-cyclohexadiene 6-methylfulvene 2-norbornene nortricyclene tricyclo[ ,4]heptane dispiro[ ]heptane 5,5-dimethyl-1,3-cyclopentadiene tricyclo[ ,7]heptane spiro[cyclopropane(1,5')bicyclo[2.1.0]pentane anti-tricyclo[ ,4]heptane anti-tricyclo[ ,4]heptane 3-(cis-ethylidene)-1-cyclopentene bicyclo[3.2.0]hept-1(5)-ene bicyclo[3.2.0]hept-1-ene styrene 5-(1-methylethylidene)-1,3-cyclopentadiene 2,3-dihydrothiophene 2,5-dihydrothiophene 1,3-dioxol-2-one cyclopropanone 1,3,5-trioxane carbon suboxide 4-methylene-2-oxetanone norbornan-7-one S

8 2-propenenitrile 1,3,5-triazine 1H-imidazole 1H-pyrazole propiolonitrile 2-methyl-1H-imidazole 2-butynedinitrile 2,3-diazabicyclo[2.2.1]-hept-2-ene cyclobutadiene 1,2,3-butatriene methylenecyclopropene methylcyclopropane 1,3-pentadiyne penta-1,4-diyne 1,2,3,4-pentatetraene 1-penten-3-yne [1.1.1]propellane bicyclo[1.1.1]pentane 1-methylcyclobutene 3,3-dimethylcyclopropene 1,2-dimethylcyclopropene methylmethylenecyclopropane ethylidenecyclopropane hex-3-en-1,5-diyne 1,4-hexadiyne bicyclo[2.2.0]hexa-2,5-diene benzvalene 1-methyl-1,3-cyclopentadiene 5-methyl-1,3-cyclopentadiene bicyclo[2.2.0]hex-2-ene 1,3-bis(methylene)cyclobutane 2-methyl-1-penten-3-yne cyclopropylidene cyclopropane ethynylcyclobutane tricyclo[ ,6]hexane bicyclo[2.1.1]hexane 1,3-dimethylbicyclo[1.1.0]butane 1,1-dimethyl-2-methylenecyclopropane 3,3-dimethylcyclobutene bicyclo[4.1.0]hepta-1,3,5-triene 5-ethenylidene-1,3-cyclopentadiene trans-1,2-diethynylcyclopropane bicyclo[3.2.0]hepta-1,4,6-triene cis-1,2-diethynylcyclopropane 5-methylenebicyclo[2.2.0]hex-2-ene spiro[3.3]hepta-2,5-diene tricyclo[ ,7]hept-3-ene tricyclo[ ,3]heptane tricyclo[ ,6]heptane 1-methyl-1,2-propadienylcyclopropane cyclopentyl acetylene (1α,4α,5β)-5-methyl-2-methylenebicyclo[2.1.0]pentane endo-2-methylene-5-methylbicyclo[2.1.0]pentane 5,5-dimethylbicyclo[2.1.0]pent-2-ene syn-tricyclo[ ,4]heptane bicyclo[4.2.0]octa-1,3,5,7-tetraene 2,4,6-octatriyne S

9 (1α,2α,5α,6α)-tricyclo[ ,5]octa-3,7-diene (1α,2β,5β,6α)-tricyclo[ ,5]octa-3,7-diene bicyclo[2.2.2]octa-2,5,7-triene 2a,2b,4a,4b-tetrahydrocyclopropa[cd]pentalene pentacyclo[ ,4.03,7.06,8]octane 7-methylenebicyclo[2.2.1]hepta-2,5-diene tricyclo[ ,8]octa-2,4-diene cycloocta-1,5-dien-3-yne cycloocta-1,3-dien-6-yne 3-methylenetetracyclo[ ,7.04,6]heptane 1,5-dihydropentalene 1-ethynyl-1-(1-propynyl)cyclopropane tetrakis(methylene)cyclobutane heptafulvene 5-methylenebicyclo[2.2.1]hept-2-ene 1,5-dimethyl-3-exo-methylenetricyclo[ ]pentane tricyclo[ ,8]oct-3-ene 1-methylnorbornadiene 2-methylnorbornadiene tricyclo[ ,8]oct-2-ene 6-methyltricyclo[ ,7]hept-3-ene 1-methyltricyclo[ ,7]hept-3-ene 7-methylenebicyclo[3.2.0]hept-1-ene bicyclo[3.3.0]octa-2,6-diene 5-methyl-3H-1,2-dithiole-3-thione 4-methyl-3H-1,2-dithiole-3-thione dihydro-2(3h)-thiophenthione 2,2-dimethylthiirane 2-methylthietane 3-methylthietane 2-methyl-1,3-dithiacyclopentane 4-methyl-1,3-dithiolane 3-methyl-1,2-dithiolane 4-methyl-1,2-dithiolane trimethylthiirane 3,3-dimethylthietane 7-thiabicyclo[4.1.0]heptane 2-(1,1-dimethylethyl)thiirane thieno[3,2-b]thiophene thieno[2,3-b]thiophene thieno[3,4-b]thiophene dithio-p-benzoquinone benzodithiete methyl-oxirane cyclopropylidenemethanone 2(3H)-furanone 1,4-dioxin 3(2H)-furanone cyclobutane-1,3-dione 1,2-cyclobutanedione 2,5-dihydrofuran 2-methyl-1-propen-1-one 3-methyleneoxetane 4-methylene-1,3-dioxolane α-trimethylethylene oxide 7-oxabicyclo[2.2.1]heptane 2-oxaspiro[3,3]heptane S

10 1,2,4-triazine 1,2,3-triazine 2-aziridinecarbonitrile 1-azetine cyclopropanimine dimethylcyanamide 3,3-dimethyldiazirine 1-pyrazoline 2-pyrazoline azetidine 1-methylaziridine 5-(dimethylamino)tetrazole 3,3-dimethyldiaziridine cyanoallene 1,1-dicyanoethane 3-methyl-1,2,4-triazine 6-methyl-1,2,4-triazine 4-methyl-1,2,3-triazine 4-aminopyrimidine 1-methyl-1H-imidazole 4-methylimidazole 4-methylpyrazole 2,5-dihydro-1H-pyrrole isopropyl isocyanide 1-methyl-5-aminopyrazole 1-methyl-3-aminopyrazole 1,1'-biaziridine N-methylazetidine 2-methyl-1,5-diazabicyclo[3.1.0]hexane pyrrole-2-carbonitrile 1-methylcyclopropene-3-carbonitrile 1-methylcyclopropanecarbonitrile a based on revised geometry presented herein. S

11 Table S2. Gas phase total energies at 0 K and enthalpies at K for compounds from ref. [1] at the W1BD level of theory. compound chlorotrifluoromethane cyanogen chloride phosgene carbonic difluoride tetrafluoromethane trichloromethane trifluoromethane hydrogen cyanide dichloromethane difluoromethane formaldehyde formic acid chloromethane methane methanol methanethiol methylamine carbon monoxide carbon dioxide carbon disulfide acetylene 1,1-dichloroethene cis-1,2-dichloroethene trans-1,2-dichloroethene 1,1-difluoroethene chloroethene fluoroethene acetonitrile ethylene acetaldehyde ethylene oxide acetic acid ethane ethanol dimethyl sulfoxide dimethylamine propyne cyclopropene propene cyclopropane acetone oxetane propylene oxide trimethylamine furan pyrrole cyclopropanecarbonitrile cyclobutene methylenecyclopropane 1-methylcyclopropene bicyclo[1.1.0]butane cis-2-butene trans-2-butene S11 E H

12 2-methyl-1-propene S

13 Table S3. Gas phase ( K, kpa) enthalpies of formation ( fh (g)) for all compounds from ref. [1] estimated at the G4 level of theory using the respective atomization energy approaches in ref. [2, 3] and ref. [4-6]. compound chlorotrifluoromethane cyanogen chloride difluorodichloromethane phosgene fluorotrichloromethane tetrachloromethane carbonic difluoride tetrafluoromethane trichloromethane trifluoromethane hydrogen cyanide dichloromethane difluoromethane formaldehyde formic acid chloromethane methane methanol methanethiol methylamine carbon monoxide carbon dioxide carbon disulfide chlorotrifluoroethene tetrachloroethene trifluoroacetonitrile tetrafluoroethene trichloroethene trifluoroethene acetylene 1,1-dichloroethene cis-1,2-dichloroethene trans-1,2-dichloroethene 1,1-difluoroethene chloroethene 1,1,1-trichloroethane fluoroethene 1,1,1-trifluoroethane acetonitrile ethylene acetaldehyde ethylene oxide acetic acid ethane ethanol dimethyl sulfoxide dimethylamine propyne cyclopropene propene cyclopropane acetone S13 fh (g) [2, ] fh (g) [4-6]

14 oxetane propylene oxide trimethylamine pyrazine pyrimidine pyridazine furan diketene thiophene pyrrole cyclopropanecarbonitrile cyclobutene methylenecyclopropane 1-methylcyclopropene bicyclo[1.1.0]butane cis-2-butene trans-2-butene 2-methyl-1-propene tetrahydrofuran butane isobutane pyridine bicyclo[1.1.0]butane-1-carbonitrile 1,3-cyclopentadiene 2-methyl-1-buten-3-yne cyclopropylacetylene bicyclo[2.1.0]pent-2-ene spiropentane bicyclo[2.1.0]pentane 1,1-dimethylcyclopropane pentane isopentane neopentane benzene fulvene 3,4-dimethylenecyclobut-1-ene tris(methylene)cyclopropane phenol aniline 2-methylpyridine bicyclo[2.1.0]pentane-1-carbonitrile hexane 2,2-dimethylbutane 2,3-dimethylbutane toluene 2,5-norbornadiene quadricyclane spiro[2,4]hepta-4,6-diene anti-tricyclo[ ,4]hept-6-ene tetracyclo[ ,4.03,5]heptane 1,2-bis(methylene)cyclobutane 3-methylenecyclopentene bicyclo[2.1.1]hex-2-ene bicyclo[2.2.0]hex-1(4)-ene benzyne phenylacetylene bicyclo[4.2.0]octa-1,3,5-triene S

15 3,6-bis(methylene)-1,4-cyclohexadiene 1-cyclopropylpenta-1,3-diyne cyclopropylbenzenea trans-bicyclo[6.1.0]nona-2,4,6-triene cis-bicyclo[4.3.0]nona-3,7-diene octahydrodicyclopropa[cd,gh]pentalene (1α,2α,4α,5α)-tricyclo[ ,4]oct-6-ene bicyclo[3.2.1]octa-2,6-diene 2,3-bis(methylene)bicyclo[2.2.0]hexane 7-methylenebicyclo[2.2.1]heptane anti-tricyclo[ ,5]octane 1-propynylbenzene hexafluorobenzene 1,2,3-trichlorobenzene 1,2,4-trichlorobenzene 1,3,5-trichlorobenzene o-dichlorobenzene m-dichlorobenzene p-dichlorobenzene o-difluorobenzene m-difluorobenzene p-difluorobenzene chlorobenzene 1-buten-3-yne bicyclo[1.1.0]but-1(3)-ene (Z)-3-penten-1-yne (Z)-hexa-1,5-diyne-3-ene (E)-hexa-1,5-diyne-3-ene 1,2-bis(methylene)cyclobutane trans-2,3,4-hexatriene cis-2,3,4-hexatriene bicyclo[2.2.0]hexane 1,1-diethynylcyclopropane bicyclo[3.2.0]hepta-2,6-diene 3-methylene-1,4-cyclohexadiene 6-methylfulvene 2-norbornene nortricyclene tricyclo[ ,4]heptane dispiro[ ]heptane 5,5-dimethyl-1,3-cyclopentadiene tricyclo[ ,7]heptane spiro[cyclopropane(1,5')bicyclo[2.1.0]pentane anti-tricyclo[ ,4]heptane anti-tricyclo[ ,4]heptane 3-(cis-ethylidene)-1-cyclopentene bicyclo[3.2.0]hept-1(5)-ene bicyclo[3.2.0]hept-1-ene styrene 5-(1-methylethylidene)-1,3-cyclopentadiene 2,3-dihydrothiophene 2,5-dihydrothiophene 1,3-dioxol-2-one cyclopropanone 1,3,5-trioxane carbon suboxide 4-methylene-2-oxetanone S

16 norbornan-7-one 2-propenenitrile 1,3,5-triazine 1H-imidazole 1H-pyrazole propiolonitrile 2-methyl-1H-imidazole 2-butynedinitrile 2,3-diazabicyclo[2.2.1]-hept-2-ene cyclobutadiene 1,2,3-butatriene methylenecyclopropene methylcyclopropane 1,3-pentadiyne penta-1,4-diyne 1,2,3,4-pentatetraene 1-penten-3-yne [1.1.1]propellane bicyclo[1.1.1]pentane 1-methylcyclobutene 3,3-dimethylcyclopropene 1,2-dimethylcyclopropene methylmethylenecyclopropane ethylidenecyclopropane hex-3-en-1,5-diyne 1,4-hexadiyne bicyclo[2.2.0]hexa-2,5-diene benzvalene 1-methyl-1,3-cyclopentadiene 5-methyl-1,3-cyclopentadiene bicyclo[2.2.0]hex-2-ene 1,3-bis(methylene)cyclobutane 2-methyl-1-penten-3-yne cyclopropylidene cyclopropane ethynylcyclobutane tricyclo[ ,6]hexane bicyclo[2.1.1]hexane 1,3-dimethylbicyclo[1.1.0]butane 1,1-dimethyl-2-methylenecyclopropane 3,3-dimethylcyclobutene bicyclo[4.1.0]hepta-1,3,5-triene 5-ethenylidene-1,3-cyclopentadiene trans-1,2-diethynylcyclopropane bicyclo[3.2.0]hepta-1,4,6-triene cis-1,2-diethynylcyclopropane 5-methylenebicyclo[2.2.0]hex-2-ene spiro[3.3]hepta-2,5-diene tricyclo[ ,7]hept-3-ene tricyclo[ ,3]heptane tricyclo[ ,6]heptane 1-methyl-1,2-propadienylcyclopropane cyclopentyl acetylene (1α,4α,5β)-5-methyl-2-methylenebicyclo[2.1.0]pentane endo-2-methylene-5-methylbicyclo[2.1.0]pentane 5,5-dimethylbicyclo[2.1.0]pent-2-ene syn-tricyclo[ ,4]heptane bicyclo[4.2.0]octa-1,3,5,7-tetraene S

17 2,4,6-octatriyne (1α,2α,5α,6α)-tricyclo[ ,5]octa-3,7-diene (1α,2β,5β,6α)-tricyclo[ ,5]octa-3,7-diene bicyclo[2.2.2]octa-2,5,7-triene 2a,2b,4a,4b-tetrahydrocyclopropa[cd]pentalene pentacyclo[ ,4.03,7.06,8]octane 7-methylenebicyclo[2.2.1]hepta-2,5-diene tricyclo[ ,8]octa-2,4-diene cycloocta-1,5-dien-3-yne cycloocta-1,3-dien-6-yne 3-methylenetetracyclo[ ,7.04,6]heptane 1,5-dihydropentalene 1-ethynyl-1-(1-propynyl)cyclopropane tetrakis(methylene)cyclobutane heptafulvene 5-methylenebicyclo[2.2.1]hept-2-ene 1,5-dimethyl-3-exo-methylenetricyclo[ ]pentane tricyclo[ ,8]oct-3-ene 1-methylnorbornadiene 2-methylnorbornadiene tricyclo[ ,8]oct-2-ene 6-methyltricyclo[ ,7]hept-3-ene 1-methyltricyclo[ ,7]hept-3-ene 7-methylenebicyclo[3.2.0]hept-1-ene bicyclo[3.3.0]octa-2,6-diene 5-methyl-3H-1,2-dithiole-3-thione 4-methyl-3H-1,2-dithiole-3-thione dihydro-2(3h)-thiophenthione 2,2-dimethylthiirane 2-methylthietane 3-methylthietane 2-methyl-1,3-dithiacyclopentane 4-methyl-1,3-dithiolane 3-methyl-1,2-dithiolane 4-methyl-1,2-dithiolane trimethylthiirane 3,3-dimethylthietane 7-thiabicyclo[4.1.0]heptane 2-(1,1-dimethylethyl)thiirane thieno[3,2-b]thiophene thieno[2,3-b]thiophene thieno[3,4-b]thiophene dithio-p-benzoquinone benzodithiete methyl-oxirane cyclopropylidenemethanone 2(3H)-furanone 1,4-dioxin 3(2H)-furanone cyclobutane-1,3-dione 1,2-cyclobutanedione 2,5-dihydrofuran 2-methyl-1-propen-1-one 3-methyleneoxetane 4-methylene-1,3-dioxolane α-trimethylethylene oxide 7-oxabicyclo[2.2.1]heptane S

18 2-oxaspiro[3,3]heptane 1,2,4-triazine 1,2,3-triazine 2-aziridinecarbonitrile 1-azetine cyclopropanimine dimethylcyanamide 3,3-dimethyldiazirine 1-pyrazoline 2-pyrazoline azetidine 1-methylaziridine 5-(dimethylamino)tetrazole 3,3-dimethyldiaziridine cyanoallene 1,1-dicyanoethane 3-methyl-1,2,4-triazine 6-methyl-1,2,4-triazine 4-methyl-1,2,3-triazine 4-aminopyrimidine 1-methyl-1H-imidazole 4-methylimidazole 4-methylpyrazole 2,5-dihydro-1H-pyrrole isopropyl isocyanide 1-methyl-5-aminopyrazole 1-methyl-3-aminopyrazole 1,1'-biaziridine N-methylazetidine 2-methyl-1,5-diazabicyclo[3.1.0]hexane pyrrole-2-carbonitrile 1-methylcyclopropene-3-carbonitrile 1-methylcyclopropanecarbonitrile a based on revised geometry presented herein. S

19 Table S4. Gas phase ( K, kpa) enthalpies of formation ( fh (g)) for compounds from ref. [1] estimated at the W1BD level of theory using the respective atomization energy approaches in ref. [2, 3] and ref. [4-6]. compound chlorotrifluoromethane cyanogen chloride phosgene carbonic difluoride tetrafluoromethane trichloromethane trifluoromethane hydrogen cyanide dichloromethane difluoromethane formaldehyde formic acid chloromethane methane methanol methanethiol methylamine carbon monoxide carbon dioxide carbon disulfide acetylene 1,1-dichloroethene cis-1,2-dichloroethene trans-1,2-dichloroethene 1,1-difluoroethene chloroethene fluoroethene acetonitrile ethylene acetaldehyde ethylene oxide acetic acid ethane ethanol dimethyl sulfoxide dimethylamine propyne cyclopropene propene cyclopropane acetone oxetane propylene oxide trimethylamine furan pyrrole cyclopropanecarbonitrile cyclobutene methylenecyclopropane 1-methylcyclopropene bicyclo[1.1.0]butane cis-2-butene S19 fh (g) [2, ] fh (g) [4-6]

20 trans-2-butene 2-methyl-1-propene S

21 G09 archive entries at the CBS-Q//B3 level of theory for methane, ethyne, ethene, ethane, propyne, propene, and benzene methane Temperature= Pressure= E(ZPE)= E(Thermal)= E(SCF)= DE(MP2)= DE(CBS)= DE(MP34)= DE(CCSD)= DE(Int)= DE(Empirical)= CBS-QB3 (0 K)= CBS-QB3 Energy= CBS-QB3 Enthalpy= CBS-QB3 Free Energy= ,1\C,0, , , \H,0, , , \H,0, , , \H,0, , , \H,0, , , \\Version=EM64L-G09RevA.02\Sta te=1-a\hf/cbsb3= \e2(cbs)/cbsb3= \cbs-int/cbsb3= \OIii/CbsB3= \MP2/CbsB4= \MP4(SDQ)/CbsB4= \MP4(SDQ)/6-31+G(d')= \QCISD(T)/6-31+G(d')= \CBSQB3= \FreqCoord= , , , , , , , , , , , , , , \PG=C01 [X(C1H4)]\NImag=0\\ ethyne Temperature= Pressure= E(ZPE)= E(Thermal)= E(SCF)= DE(MP2)= DE(CBS)= DE(MP34)= DE(CCSD)= DE(Int)= DE(Empirical)= CBS-QB3 (0 K)= CBS-QB3 Energy= CBS-QB3 Enthalpy= CBS-QB3 Free Energy= \1\GINC-CL1N048\Mixed\CBS-QB3\CBS-QB3\C2H2\KFOREST\27-Dec-2010\0\\# C BS-QB3\\<< job name >>\\0,1\C,0, , , \C,0, , , \H,0, , , \H,0, , , \\Vers ion=em64l-g09reva.02\state=1-sg\hf/cbsb3= \e2(cbs)/cbsb3= \CBS-Int/CbsB3= \OIii/CbsB3= \MP2/CbsB4= \MP4(SDQ)/CbsB4= \MP4(SDQ)/6-31+G(d')= \QCISD( T)/6-31+G(d')= \CBSQB3= \FreqCoord= , , , , , , , , , , , \PG=C*V [C*(H1C1C1H1)]\NImag=0\\ ethene Temperature= Pressure= E(ZPE)= E(Thermal)= E(SCF)= DE(MP2)= DE(CBS)= DE(MP34)= DE(CCSD)= DE(Int)= DE(Empirical)= CBS-QB3 (0 K)= CBS-QB3 Energy= CBS-QB3 Enthalpy= CBS-QB3 Free Energy= \1\GINC-CL1N119\Mixed\CBS-QB3\CBS-QB3\C2H4\KFOREST\27-Dec-2010\0\\# C BS-QB3\\<< job name >>\\0,1\C,0, , , \C,0, , , \H,0, ,1.153 S21

22 , \H,0, , , \H, 0, , , \H,0, , , \\Version=EM64L-G09RevA.02\State=1-A\HF/CbsB3= \E2(CBS)/CbsB3= \CBS-Int/CbsB3= \OIii/CbsB3= \MP2/CbsB4= \MP4(SDQ)/CbsB4= \MP4(SDQ)/6-31+G(d') = \QCISD(T)/6-31+G(d')= \CBSQB3= \FreqCoo rd= , , , , , , , , , , , , , , , , , \PG=C01 [X(C2H4)]\NImag=0\\ ethane Temperature= Pressure= E(ZPE)= E(Thermal)= E(SCF)= DE(MP2)= DE(CBS)= DE(MP34)= DE(CCSD)= DE(Int)= DE(Empirical)= CBS-QB3 (0 K)= CBS-QB3 Energy= CBS-QB3 Enthalpy= CBS-QB3 Free Energy= \1\GINC-CL1N119\Mixed\CBS-QB3\CBS-QB3\C2H6\KFOREST\27-Dec-2010\0\\# C BS-QB3\\<< job name >>\\0,1\C,0, , , \C,0, , , \H,0, , , \H,0, , , \H,0, , , \H,0, , , \H,0, , , \H,0, , , \\Version=EM64L-G09RevA.02\State=1-A\H F/CbsB3= \E2(CBS)/CbsB3= \CBS-Int/CbsB3= \O Iii/CbsB3= \MP2/CbsB4= \MP4(SDQ)/CbsB4= \M P4(SDQ)/6-31+G(d')= \QCISD(T)/6-31+G(d')= \CBSQB3= \FreqCoord= , , , , , , , , , , , , , , , , , , , , , , , \PG=C01 [X(C2H6)]\NImag=0\\ propyne Temperature= Pressure= E(ZPE)= E(Thermal)= E(SCF)= DE(MP2)= DE(CBS)= DE(MP34)= DE(CCSD)= DE(Int)= DE(Empirical)= CBS-QB3 (0 K)= CBS-QB3 Energy= CBS-QB3 Enthalpy= CBS-QB3 Free Energy= \1\GINC-CL1N119\Mixed\CBS-QB3\CBS-QB3\C3H4\KFOREST\27-Dec-2010\0\\# C BS-QB3\\<< job name >>\\0,1\C,0, , , \C,0, , , \H,0, , , \H,0, , , \H,0, , , \C,0, , , \H,0, , , \\Version=EM64L-G 09RevA.02\State=1-A\HF/CbsB3= \E2(CBS)/CbsB3= \CBS -Int/CbsB3= \OIii/CbsB3= \MP2/CbsB4= \MP4(SD Q)/CbsB4= \MP4(SDQ)/6-31+G(d')= \QCISD(T)/6-31+G (d')= \cbsqb3= \freqcoord= , , , , , , , S22

23 , , , , , , , , , , , , , \PG=C01 [X(C3H4)]\NImag =0\\ propene Temperature= Pressure= E(ZPE)= E(Thermal)= E(SCF)= DE(MP2)= DE(CBS)= DE(MP34)= DE(CCSD)= DE(Int)= DE(Empirical)= CBS-QB3 (0 K)= CBS-QB3 Energy= CBS-QB3 Enthalpy= CBS-QB3 Free Energy= \1\GINC-CL1N048\Mixed\CBS-QB3\CBS-QB3\C3H6\KFOREST\27-Dec-2010\0\\# C BS-QB3\\<< job name >>\\0,1\C,0, , , \C,0, , , \C,0, , , \H,0, , , \H,0, , , \H,0, , , \H,0, , , \H,0, , , \H,0, , , \\Versi on=em64l-g09reva.02\state=1-a\hf/cbsb3= \e2(cbs)/cbsb3= \CBS-Int/CbsB3= \OIii/CbsB3= \MP2/CbsB4= \MP4(SDQ)/CbsB4= \MP4(SDQ)/6-31+G(d')= \QCIS D(T)/6-31+G(d')= \CBSQB3= \FreqCoord= , , , , , , , , , , , , , , , , , , , , , , , , , , \PG=C01 [X (C3H6)]\NImag=0\\ benzene Temperature= Pressure= E(ZPE)= E(Thermal)= E(SCF)= DE(MP2)= DE(CBS)= DE(MP34)= DE(CCSD)= DE(Int)= DE(Empirical)= CBS-QB3 (0 K)= CBS-QB3 Energy= CBS-QB3 Enthalpy= CBS-QB3 Free Energy= \1\GINC-CL1N102\Mixed\CBS-QB3\CBS-QB3\C6H6\KFOREST\27-Dec-2010\0\\# C BS-QB3\\<< job name >>\\0,1\C,0, , , \C,0, , , \C,0, , , \C,0, , , \C,0, , , \C,0, , , \H,0, , , \H,0, , , \H,0, , , \H,0, , , \H,0, , , \H,0, , , \\Version=EM64L-G09RevA.02\State=1-AG\HF/CbsB3= \E2 (CBS)/CbsB3= \CBS-Int/CbsB3= \OIii/CbsB3= \MP2 /CbsB4= \MP4(SDQ)/CbsB4= \MP4(SDQ)/6-31+G(d')= \QCISD(T)/6-31+G(d')= \CBSQB3= \FreqCo ord= , , , , , , , , , , , , , , , S23

24 , , , , , , , , , , , , , , , , , , , , \PG=CI [X(C6H6)]\NImag=0\\ S24

25 Revised G09 archive entry and visualized geometry at the Gaussian-4 (G4) level of theory for cyclopropylbenzene Temperature= Pressure= E(ZPE)= E(Thermal)= E(CCSD(T))= E(Empiric)= DE(Plus)= DE(2DF)= E(Delta-G3XP)= DE(HF)= G4(0 K)= G4 Energy= G4 Enthalpy= G4 Free Energy= \1\GINC-CL1N142\Mixed\G4\G4\C9H10\KFOREST\30-Dec-2010\0\\# G4\\<< job name >>\\0,1\C,0, , , \C,0, , , \C,0, , , \C,0, , , \C,0, , , \C,0, , , \H,0, , , \H,0, , , \H,0, , , \H,0, , , \H,0, , , \C,0, , , \C,0, , , \C,0, , , \H,0, , , \H,0, , , \H,0, , , \H,0, , , \H,0, , , \\Version=EM64L-G09RevA.02\State=1-A\MP2/GTBas1= \M P4/GTBas1= \CCSD(T)/G3Bas1= \MP2/GTBas2= \MP4/GTBas2= \MP2/GTBas3= \MP4/GTBas3= \HF/GTLargeXP= \MP2/GTLargeXP= \HF/GFHFB1= \HF/GFHFB2= \G4= \FreqCoord= , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , \PG=C01 [X(C9H10)]\NIma g=0\\ S25

26 Visualization of optimized Gaussian-4 (G4) geometries for all compounds as published in ref. [1]: Note: Geometries visualized using Gabedit v [7] (bond orders assigned automatically by the software while reading the G09 output files, and may not be accurate representations of actual bond orders). chlorotrifluoromethane cyanogen chloride difluorodichloromethane phosgene fluorotrichloromethane tetrachloromethane S26

27 carbonic difluoride tetrafluoromethane trichloromethane trifluoromethane hydrogen cyanide dichloromethane difluoromethane S27

28 formaldehyde formic acid chloromethane methane methanol methanethiol methylamine S28

29 carbon monoxide carbon dioxide carbon disulfide chlorotrifluoroethene tetrachloroethene trifluoroacetonitrile tetrafluoroethene S29

30 trichloroethene trifluoroethene acetylene 1,1-dichloroethene cis-1,2-dichloroethene trans-1,2-dichloroethene 1,1-difluoroethene S30

31 chloroethene 1,1,1-trichloroethane fluoroethene 1,1,1-trifluoroethane acetonitrile ethylene acetaldehyde S31

32 ethylene oxide acetic acid ethane ethanol dimethyl sulfoxide dimethylamine propyne S32

33 cyclopropene propene cyclopropane acetone oxetane propylene oxide trimethylamine S33

34 pyrazine pyrimidine pyridazine furan diketene thiophene pyrrole S34

35 cyclopropanecarbonitrile cyclobutene methylenecyclopropane 1-methylcyclopropene bicyclo[1.1.0]butane cis-2-butene trans-2-butene S35

36 2-methyl-1-propene tetrahydrofuran butane isobutane pyridine bicyclo[1.1.0]butane-1-carbonitrile 1,3-cyclopentadiene S36

37 2-methyl-1-buten-3-yne cyclopropylacetylene bicyclo[2.1.0]pent-2-ene spiropentane bicyclo[2.1.0]pentane 1,1-dimethylcyclopropane pentane S37

38 isopentane neopentane benzene fulvene 3,4-dimethylenecyclobut-1-ene tris(methylene)cyclopropane phenol S38

39 aniline 2-methylpyridine bicyclo[2.1.0]pentane-1-carbonitrile hexane 2,2-dimethylbutane 2,3-dimethylbutane toluene S39

40 2,5-norbornadiene quadricyclane spiro[2,4]hepta-4,6-diene anti-tricyclo[ ,4]hept-6-ene tetracyclo[ ,4.03,5]heptane 1,2-bis(methylene)cyclobutane 3-methylenecyclopentene S40

41 bicyclo[2.1.1]hex-2-ene bicyclo[2.2.0]hex-1(4)-ene benzyne phenylacetylene bicyclo[4.2.0]octa-1,3,5-triene 3,6-bis(methylene)-1,4-cyclohexadiene 1-cyclopropylpenta-1,3-diyne S41

42 cyclopropylbenzene trans-bicyclo[6.1.0]nona-2,4,6-triene cis-bicyclo[4.3.0]nona-3,7-diene octahydrodicyclopropa[cd,gh]pentalene (1α,2α,4α,5α)-tricyclo[ ,4]oct-6-ene bicyclo[3.2.1]octa-2,6-diene 2,3-bis(methylene)bicyclo[2.2.0]hexane S42

43 7-methylenebicyclo[2.2.1]-heptane anti-tricyclo[ ,5]octane 1-propynylbenzene hexafluorobenzene 1,2,3-trichlorobenzene 1,2,4-trichlorobenzene 1,3,5-trichlorobenzene S43

44 o-dichlorobenzene m-dichlorobenzene p-dichlorobenzene o-difluorobenzene m-difluorobenzene p-difluorobenzene chlorobenzene S44

45 1-buten-3-yne bicyclo[1.1.0]but-1(3)-ene (Z)-3-penten-1-yne (Z)-hexa-1,5-diyne-3-ene (E)-hexa-1,5-diyne-3-ene 1,2-bis(methylene)cyclobutane S45

46 trans-2,3,4-hexatriene cis-2,3,4-hexatriene bicyclo[2.2.0]hexane 1,1-diethynylcyclopropane bicyclo[3.2.0]hepta-2,6-diene 3-methylene-1,4-cyclohexadiene S46

47 6-methylfulvene 2-norbornene nortricyclene tricyclo[ ,4]-heptane dispiro[ ]heptane 5,5-dimethyl-1,3-cyclopentadiene tricyclo[ ,7]heptane S47

48 spiro[cyclopropane(1,5')bicyclo[2.1.0]pentane] anti-tricyclo[ ,4]heptane anti-tricyclo[ ,4]heptane 3-(cis-ethylidene)-1-cyclopentene bicyclo[3.2.0]hept-1(5)-ene bicyclo[3.2.0]hept-1-ene styrene S48

49 5-(1-methylethylidene)-1,3-cyclopentadiene 2,3-dihydrothiophene 2,5-dihydrothiophene 1,3-dioxol-2-one cyclopropanone 1,3,5-trioxane carbon suboxide S49

50 4-methylene-2-oxetanone norbornan-7-one 2-propenenitrile 1,3,5-triazine 1H-imidazole 1H-pyrazole propiolonitrile S50

51 2-methyl-1H-imidazole 2-butynedinitrile 2,3-diazabicyclo[2.2.1]-hept-2-ene cyclobutadiene 1,2,3-butatriene methylenecyclopropene methylcyclopropane S51

52 1,3-pentadiyne penta-1,4-diyne 1,2,3,4-pentatetraene 1-penten-3-yne [1.1.1]propellane bicyclo[1.1.1]pentane 1-methylcyclobutene S52

53 3,3-dimethylcyclopropene 1,2-dimethylcyclopropene methylmethylenecyclopropane ethylidenecyclopropane hex-3-en-1,5-diyne 1,4-hexadiyne S53

54 bicyclo[2.2.0]hexa-2,5-diene benzvalene 1-methyl-1,3-cyclopentadiene 5-methyl-1,3-cyclopentadiene bicyclo[2.2.0]hex-2-ene 1,3-bis(methylene)cyclobutane 2-methyl-1-penten-3-yne S54

55 cyclopropylidene cyclopropane ethynylcyclobutane tricyclo[ ,6]hexane bicyclo[2.1.1]hexane 1,3-dimethylbicyclo[1.1.0]butane 1,1-dimethyl-2-methylenecyclopropane 3,3-dimethylcyclobutene S55

56 bicyclo[4.1.0]hepta-1,3,5-triene 5-ethenylidene-1,3-cyclopentadiene trans-1,2-diethynylcyclopropane bicyclo[3.2.0]hepta-1,4,6-triene cis-1,2-diethynylcyclopropane bicyclo[2.2.0]hex-2-ene,5-methylene spiro[3.3]hepta-2,5-diene S56

57 tricyclo[ ,7]hept-3-ene tricyclo[ ,3]heptane tricyclo[ ,6]heptane (1-methyl-1,2-propadienyl)cyclopropane cyclopentyl acetylene (1α, 4α, 5β)-5-methyl-2-methylenebicyclo[2.1.0]pentane endo-2-methylene-5-methylbicyclo[2.1.0]pentane S57

58 5,5-dimethylbicyclo[2.1.0]pent-2-ene syn-tricyclo[ ,4]heptane bicyclo[4.2.0]octa-1,3,5,7-tetraene 2,4,6-octatriyne (1α,2α,5α,6α)-tricyclo[ ,5]octa-3,7-diene (1α,2β,5β,6α)-tricyclo[ ,5]octa-3,7-diene S58

59 bicyclo[2.2.2]octa-2,5,7-triene 2a,2b,4a,4b-tetrahydrocyclopropa[cd]pentalene pentacyclo[ ,4.03,7.06,8]octane 7-methylenebicyclo[2.2.1]hepta-2,5-diene tricyclo[ ,8]octa-2,4-diene cycloocta-1,5-dien-3-yne cycloocta-1,3-dien-6-yne S59

60 3-methylenetetracyclo[ ,7.04,6]heptane 1,5-dihydropentalene 1-ethynyl-1-(1-propynyl)cyclopropane tetrakis(methylene)cyclobutane heptafulvene 5-methylenebicyclo[2.2.1]hept-2-ene 1,5-dimethyl-3-exo-methylenetricyclo[ ]pentane S60

61 tricyclo[ ,8]oct-3-ene 1-methylnorbornadiene 2-methylnorbornadiene tricyclo[ ,8]oct-2-ene 6-methyltricyclo[ ,7]hept-3-ene 1-methyltricyclo[ ,7]hept-3-ene 7-methylenebicyclo[3.2.0]hept-1-ene S61

62 bicyclo[3.3.0]octa-2,6-diene 5-methyl-3H-1,2-dithiole-3-thione 3H-1,2-dithiole-3-thione, 4-methyl- dihydro-2(3h)-thiophenthione 2,2-dimethylthiirane 2-methylthietane 3-methylthietane S62

63 2-methyl-1,3-dithiacyclopentane 4-methyl-1,3-dithiolane 3-methyl-1,2-dithiolane 4-methyl-1,2-dithiolane trimethylthiirane 3,3-dimethylthietane 7-thiabicyclo[4.1.0]heptane S63

64 2-(1,1-dimethylethyl)thiirane thieno[3,2-b]thiophene thieno[2,3-b]thiophene thieno[3,4-b]thiophene dithio-p-benzoquinone benzodithiete methyloxirane S64

65 cyclopropylidenemethanone 2(3H)-furanone 1,4-dioxin 3(2H)-furanone cyclobutane-1,3-dione 1,2-cyclobutanedione 2,5-dihydrofuran S65

66 2-methyl-1-propen-1-one 3-methyleneoxetane 4-methylene-1,3-dioxolane α-trimethylethylene oxide 7-oxabicyclo[2.2.1]heptane 2-oxaspiro[3,3]heptane 1,2,4-triazine S66

67 1,2,3-triazine 2-aziridinecarbonitrile 1-azetine cyclopropanimine dimethylcyanamide 3,3-dimethyldiazirine 1-pyrazoline S67

68 2-pyrazoline azetidine 1-methylaziridine 5-(dimethylamino)tetrazole 3,3-dimethyldiaziridine cyanoallene 1,1-dicyanoethane S68

69 3-methyl-1,2,4-triazine 6-methyl-1,2,4-triazine 4-methyl-1,2,3-triazine pyrimidine, 4-amino-, 1h-imidazole, 1-methyl- 4-methylimidazole 4-methylpyrazole S69

70 2,5-dihydro-1H-pyrrole isopropyl isocyanide 1-methyl-5-aminopyrazole 1-methyl-3-aminopyrazole 1,1'-biaziridine N-methylazetidine 2-methyl-1,5-diazabicyclo[3.1.0]hexane S70

71 pyrrole-2-carbonitrile 1-methylcyclopropene-3-carbonitrile 1-methylcyclopropanecarbonitrile S71