Organic Radical Cations, Neutral Radicals, Cations, and Anions

The ionization energy, IP, is listed after the reaction. The bond dissociation energy, DE, for the radical cation is given between the corresponding fragments.

Propane, 2-methylbutane, 2,2-dimethylbutane, Simple List

   Propane
propane, CH3CH2CH3 -> propane radical cation, CH3CH2CH3+IP= 1024 kJ/mol

propane radical cation, CH3CH2CH3
+• ->
propyl cation, CH3CH2CH2+ DE= 162 kJ/mol H•
propyl radical, CH3CH2CH2 DE= 738 kJ/mol H+
isopropyl cation, (CH3)2CH+ DE= 121 kJ/mol H•
isopropyl radical, (CH3)2CH• DE= 720 kJ/mol H+
ethyl cation, CH3CH2+ DE= 146 kJ/mol methyl radical, CH3
ethyl radical, CH3CH2 DE= 327 kJ/mol methyl cation, CH3+

   2-Methylbutane
2-methylbutane, (CH3)2CHCH2CH3 -> 2-methylbutane radical cation, (CH3)2CHCH2CH3+IP= 931 kJ/mol

2-methylbutane radical cation, (CH3)2CHCH2CH3+• ->
isobutyl radical, (CH3)2CHCH2 DE= 418 kJ/mol methyl cation, CH3+
t-butyl cation, (CH3)3C+ (Note) DE= 62 kJ/mol methyl radical, CH3
isopropyl cation, (CH3)2CH+ DE= 122 kJ/mol ethyl radical, CH3CH2
isopropyl radical, (CH3)2CH• DE= 205 kJ/mol ethyl cation, CH3CH2+
Note: the isobutyl cation, (CH3)2CHCH2+, rearranges to the t-butyl cation.

   2,2-Dimethylbutane
2,2-dimethylbutane, (CH3)3CCH2CH3 -> 2,2-dimethylbutane radical cation, (CH3)3CCH2CH3+IP= 900 kJ/mol

2,2-dimethylbutane radical cation, CH3C(CH3)2CH2CH3+• ->
t-butyl radical, (CH3)3C• DE= 218 kJ/mol ethyl cation, CH3CH2+
t-butyl cation, (CH3)3C+ DE= 76 kJ/mol ethyl radical, CH3CH2
isopentyl radical, (CH3)2C(•)CH2CH3 DE= 420 kJ/mol methyl cation, CH3+
isopentyl cation, (CH3)2C(+)CH2CH3 DE= 85 kJ/mol methyl radical, CH3

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Reactive Intermediates

Hydrocarbons


C1
methane, CH4     methylene singlet, CH2     methylene triplet, CH2**     methyl radical, CH3     methyl cation, CH3+     methyl anion, CH3-    
C2
ethane, CH3CH3     ethane radical cation, CH3CH3+•     ethyl radical, CH3CH2     ethyl cation, CH3CH2+     ethyl anion, CH3CH2-    
ethylene, CH2=CH2     ethylene radical cation, CH2=CH2+•     vinyl radical, CH2=CH•     vinyl cation, CH2=CH+    
acetylene, HCCH     deH-acetylene radical, HCC•     acetylene anion, HCC-    
C3
propane, CH3CH2CH3     propane radical cation, CH3CH2CH3+•     propyl radical, CH3CH2CH2     propyl cation, CH3CH2CH2+    
cyclopropane, CH2(CH2)CH2     cyclopropane radical, CH2(CH2)CH2    
isopropyl cation, (CH3)2CH+     isopropyl radical, (CH3)2CH•    
propene, CH2=CHCH3     propene radical cation, CH2=CHCH3+•     1-deH-1-propene radical, CH3CH=CH•     2-deH-propene cation, CH2=C(+)CH3     1-deH-1-propene cation, CH3CH=CH+    
    allyl cation, CH2=CHCH2+     allyl radical, CH2=CHCH2     allyl anion, CH2=CHCH2-    
C4
butane, CH3CH2CH2CH3     butane radical cation, CH3CH2CH2CH3+•     1-deH-butane radical, CH3CH2CH2CH2•    
2-deH-butane radical, CH3CH2CH(•)CH3     1-deH-butane cation, CH3CH2CH2CH2+     2-deH-butane cation, CH3CH2CH(+)CH3    
2-methylpropane, (CH3)3CH     2-methylpropane radical cation, (CH3)3CH+•    
isobutyl cation, (CH3)2CHCH2+     isobutyl radical, (CH3)2CHCH2    
2-methylpropene, (CH3)2C=CH2     2-methylpropene radical cation, (CH3)2C=CH2+•     2-deH-1-methylcyclopropane cation, CH2(CH+)CHCH3     3-deH-butene cation, CH2=CHC(+)HCH3     2-deH-methylpropene cation, CH2=CH(CH3)CH2+     1-deH-1-methylcyclopropane cation, CH2(CH2)C(+)CH3
t-butyl radical, (CH3)3C•     t-butyl cation, (CH3)3C+    
C5
2-methylbutane, (CH3)2CHCH2CH3     2-methylbutane radical cation, (CH3)2CHCH2CH3+•     isopentyl radical, (CH3)2C(•)CH2CH3    
isopentyl cation, (CH3)2C(+)CH2CH3     1-pentene, H2C=CHCH2CH2CH3     1-pentene radical cation, H2C=CHCH2CH2CH3+•    
C6
2-methylpentane radical cation, CH3CH(CH3)CH2CH2CH3+•    
2,2-dimethylbutane, (CH3)3CCH2CH3     2,2-dimethylbutane radical cation, (CH3)3CCH2CH3+•    

Oxygen: Alcohols, Ethers, Aldehydes, Ketones, and Acids

C1
methanol, CH3OH     methanol radical cation, CH3OH+•     methoxy radical, CH3O•     methylperoxyl radical, CH3OO•    
methoxy cation, CH3O+     methanol onium cation, CH3OH2+ methoxy anion, CH3O-     1-deH-methanol radical, CH2•O    
formaldehyde, CH2O     formyloxonium cation, CH2OH+     deH-formaldehyde cation, HCO+    
deH-formaldehyde anion, HCO-     deH-formaldehyde radical, HCO•    
formic acid, HCOOH     1-deH-formic acid radical, HOOC•     formate anion , HCOO-    
C2
ethanol, CH3CH2OH     O-deH-ethanol radical, CH3CH2O•     ethoxy anion, CH3CH2O-     methyl acylium cation, CH3CO+    
ethyleneoxide, C2H4O     deH-ethyleneoxide cation, C2H3O+    
dimethylether radical, CH3OCH2     dimethylether cation, CH3OCH2+    
vinyl alcohol, CH2=CHOH     vinyl alcohol radical cation, CH2=CHOH+•     vinyloxy radical, CH2=CHO•     vinyloxy anion, CH2=CHO-    
1-deH-acetaldehyde cation, CH3CO+     1-deH-acetaldehyde radical, CH3CO•    
2-deH-acetaldehyde cation, O=CHCH2+     2-deH-acetaldehyde radical, O=CHCH2
acetic acid, CH3COOH     acetic acid radical, CH3COO•     acetate anion, CH3COO-    
deH-acetic acid radical, HOOCCH2     deH-acetic acid cation, HOOCCH2+     O-deH-acetic acid cation, CH3COO+    
C3
propanol, CH3CH2CH2OH     propanol radical cation, CH3CH2CH2OH+•     1-deH-propanol radical, CH3CH2CH•OH    
1-deH-propanol cation, CH3CH2CH(+)OH     2-deH-propanol radical, CH3CH•CH2OH     2-deH-propanol cation, CH3CH(+)CH2OH    
3-deH-propanol cation, CH2(+)CH2CH2OH     isopropanol, (CH3)2CHOH     isopropanol radical cation, (CH3)2CHOH+•    
methylethylether, CH3OCH2CH3     methylethylether radical cation, CH3OCH2CH3+•    
deH-methylethylether radical, CH3CH2OCH2     deH-methylethylether cation, CH3CH2OCH2+    
propanal radical cation, CH3CH2CO+•     1-deH-propanal cation, CH3CH2CO+     1-deH-propanal radical, CH3CH2CO•    
acetone, CH3C=OCH3     deH-propanone cation, CH3C=OCH2+     deH-propanone radical, CH3C=OCH2    
propenol radical cation, H2C=COHCH3+•     allyl alcohol radical, HOCH=CHCH2    
methylacetate, CH3COOCH3     methylacetate radical cation, CH3COOCH3+•    
methyl-deH-acetate radical, CH3OOCCH2     methyl-deH-acetate cation, CH3OOCCH2+    
propanoic acid, CH3CH2COOH     propanoic acid radical, CH3CH2COO•    
2-deH-propanoic acid radical, CH3CH•COOH     2-deH-propanoic acid cation, CH3CH(+)COOH    

C4-C5 Alcohols, Ethers
C4
2-methylpropanol, (CH3)2CHCH2OH     2-methylpropanol radical cation, (CH3)2CHCH2OH+•    
    2-deH-2-methylpropanol radical, (CH3)2C•CH2OH     2-methylpropoxy radical, (CH3)2CHCH2O•    
t-butanol, (CH3)3COH     t-butanol radical cation, (CH3)3COH+•    
t-butyloxy cation, (CH3)3CO+     2-deH-isopropylmethylether cation, (CH3)2C(+)OCH3     t-butyloxy radical, (CH3)3CO•    
diethylether, CH3CH2OCH2CH3     diethylether radical cation, CH3CH2OCH2CH3+•    
ethylvinylether, CH3CH2OCH=CH2     ethylvinylether radical cation, CH3CH2OCH=CH2+•    
C5
methyl-t-butylether, (CH3)3COCH3     methyl-t-butylether radical cation, (CH3)3COCH3+•    

C4-C5 Aldehydes, Ketones, Carboxylic Acids
C4
butyraldehyde, CH3CH2CH2CHO     butyraldehyde radical cation, CH3CH2CH2CHO+•    
    1-deH-butyraldehyde radical, CH3CH2CH2CO•     1-deH-butyraldehyde cation, CH3CH2CH2CO+    
2-butanone, CH3CH2COCH3     2-butanone radical cation, CH3CH2COCH3+•    
methylpropionate, CH3CH2COOCH3     methylpropionate radical cation, CH3CH2COOCH3+•    
C5
2-pentanone, CH3CH2CH2COCH3     2-pentanone radical cation, CH3CH2CH2COCH3+•    
    pentenol radical cation, CH3COH=CH2CH2CH2+•    

Nitrogen

methylamine, CH3NH2     N-deH-methylamine radical, CH3NH•     methaniminonium ion, CH2NH2+    methylamide anion, CH3NH-     methylammonium radical, CH3NH3•    
2-aminobutane, CH3CH(NH2)CH2CH3     2-aminopropyl radical, CH3CH(NH2)CH2     imine, CH2=NH    
N-deH-ethanimine radical, CH3CH=N•     acetonitrile, CH3CN     1-deH-acetonitrile radical, NCCH2     1-deH-acetonitrile anion, NCCH2-    
propylimmonium cation, CH3CH2CH=NH2+     2-aminopropyl cation, CH3CH(NH2)CH2+    
dimethylamine, CH3NHCH3     dimethylamine radical cation, CH3NHCH3+•     dimethylamine radical, CH3N•CH3    
N-methylmethaniminonium cation, CH3NH=CH2+    
formamide, HCONH2     formamidate anion, HCONH-     N-methylacetamide, CH3C=ONHCH3    
N-methylacetamide radical cation, CH3C=ONHCH3+•     N-methylacetamide radical, CH3C=ON•CH3    
N-methylacetamide cation, CH3C=ON(+)CH3    
N,N-dimethylacetamide, CH3C=ON(CH3)2     N,N-dimethylacetamide radical cation, CH3C=ON(CH3)2+•    

Halogens

difluorocarbene singlet, CF2     methylfluoride cation, CH2F+     methylchloride cation, CH2Cl+     methylchloride anion, CH2Cl-    
ethylfluoride, CH3CH2F     1,1-difluoroethane, CH3CHF2     ethylfluoride radical cation, CH3CH2F+•    
fluoroethylene, CH2CHF     1-deH-1-fluoroethylene anion, CH2CF-    
chloroethane, CH3CH2Cl     1-deH-1-chloroethane radical, CH3CH(•)Cl     chloroethylene, CH2CHCl    
bromooethane, CH3CH2Br     1-deH-1-bromoethane radical, CH3CH(•)Br    
anti-dichloroethane radical cation, anti-C2H4Cl2+
    allylchloride radical, ClCH=CHCH2     1-chloropropane radical, ClCH2CH•CH3
chloroacetic acid, ClCH2COOH     chloroacetate anion, ClCH2COO-    

Allylic

allyl cation, CH2=CHCH2+     allyl radical, CH2=CHCH2     allyl-     allylalcohol radical     allylchloride radical     1-chloropropane radical

Small Radicals and Ions

OH radical     HOO radical     HCO3 radical     CO3- radical    

Stable Neutral Molecules

Hydrides: H2O     HCN     HNCO     HOCN     HNCS     HSCN     HF     HCl    

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This work was supported by an Academic Research Infrastructure Grant from the National Science Foundation, no. 9512457.

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