Compound Bond Dissociation Enthalpy (kcal/mol) Bond (C-Y ...lectka.chemistry.jhu.edu/assets/Bond-Strength-Files/C-H-bond-str.pdfR = 4-CH 3OPh heterolysis 66.9 homolysis 69.4 R = 4-CH

Compound Bond Dissociation Enthalpy (kcal/mol)Bond (C-Y) Energy Theory Level

R = H C-H 79.5R = Me3C 79.4R = Ph3C 77.2R = Me3Si 82.5R = Et3Si 81.2R = Ph3Si 80.6R = PhSO2CH4 99R = PhSO2CH2SiMe3 99.4R = PhSO2CH2SiPh3 97.4R = PhSO2CH(SiMe3)2 96.5R = PhS(O)(=NSO2Tol)CH3 103.1R = PhS(O)(=NSO2Tol)CH(SiMe3)2 99.8R = PhSO2CH2Ph 90.2R = PhSO2CH(CH=CH2)(SiMe3) 91.1

Zhang, S.; Zhang, X-M.; Bordwell, F. G. J. Am. Chem. Soc. 1995, 117, 602-606.

R = PhCH2 C-H heterol. 64.2homolysis 67.9

R = 4-CH3OPh heterolysis 66.9homolysis 69.4

R = 4-CH3Ph heterolysis 67.5homolysis 69.2

R = Ph heterolysis 68.8homolysis 69.2

R = 4-ClPh heterolysis 70.2homolysis 69.1

R = 4-BrPh heterolysis 70.4homolysis 69.2

R = 4-CF3Ph heterolysis 72.6homolysis 69.5

R = H C-H heterol. 69.3homolysis 69.4

R = CH3 heterolysis 69.9homolysis 68.8

R = CH3 C-H heterol. 81.1homolysis 73.7

Chem. Eur. J. 2003, 9(4) , 871-880

H R

N

H H

R

CONH2

N

H H

R

CO2EtEtO2C

H3C CH3

N

H H

R


C-H 105.5 B3LYP-LLM105.5 B3LYP-MLM1105.5 B3LYP-MLM2105.8 B3LYP-HLM104.9 G3105.3 G3MP2104.9 Experimental

89.3 B3LYP-LLM89.4 B3LYP-MLM190.1 B3LYP-MLM290.6 B3LYP-HLM91.1 G393.1 G3MP288.5 Experimental




C-O 32.7 B3P86-LLM35.9 B3P86-MLM34.1 B3P86-MLM32.4 G3MP232.2 G332.7 Experimental

Pratt, D. A.; Mills, J. H.; Porter, N. A. J. Am. Chem. Soc. 2003, 125 , 5801-581 Reference includes radical stabilization energies

H3C H

H

H

H

H

H3C OO


C-R trans, cis dissociated radical 19.6, 23.1 B3P86-HLM

R = H as trans or cis 83.4, 87.0 B3LYP-HLM

20.5, 21.3 B3P86-HLMR = H 84.0, 84.9 B3LYP-HLM

7.9, 7.4 B3P86-HLMR = H 73.1, 72.7 B3LYP-HLM

8.4, B3P86-HLMR = H 73.5, B3LYP-HLM

14.2, 77.4 B3P86-HLMR = H 15.3, 78.5 B3LYP-HLM

14.6, 77.7 B3P86-HLMR = H 15.7, 78.8 B3LYP-HLM

4.2 B3P86-HLMR = H 69.8 B3LYP-HLM

6.0 B3P86-HLMR = H 71.5 B3LYP-HLM

9.8, 11.2 B3P86-HLMR = H 72.9, 74.3 B3LYP-HLM

11.7, 12.9 B3P86-HLMR = H 75.1, 76.3 B3LYP-HLM

Pratt, D. A.; Mills, J. H.; Porter, N. A. J. Am. Chem. Soc. 2003, 125 , 5801-5810

R = OO

R = OO

R = OO

R = OO

R = OO

R = OO

R = OO

R = OO

R = OO

R = OO

Me MeR

Me

MeR

Me

R

Me

R

Me Me

R

Me Me

R

Me

Me

MeMe

R

MeMe

R

MeR

Me

MeMe

R


C-H Syn 100.4 All Calculated with DFTAnti 96.5 (RO)B3LYP/6-311G

Syn 100.2Anti 96.7

Syn 100.2Anti 96.7

Syn 100.1Anti 96.8

Syn 104.3Anti 105.0

Syn 100.2Anti 96.0

Syn 102.2Anti 101.9

Syn 99.8Anti 96.6

Syn 102.2Anti 99.7

Syn 100.8Anti 95.3

Syn 101.6Anti 101.0

Syn 100.1Anti 96.6

Syn 100.8Anti 100.9

Syn 99.6Anti 96.6

Syn 101.8Anti 99.3

Syn 100.8Anti 95.4

Urata, S.; Uchimaru, T.; Chandra, A. K.; Takada, A.; Sekiya, A. J. Chem. Kinetics 2002, 34 , 524-530

O

OHCF3

O

OHC2F5

O

OHC3F7

O

OHC4F9

O

OH H

FF

O

OHCHF2

O

OH CHF2

FF

O

OH CHF2

FF

O

OH CF3

HF

O

OH CF3

HF

O

OHCHF2

FF

FFO

OHCHF2

FF

FF

O

OHCF3

FF

FH

O

OHCF3

FF

FH

O

OHCF3

FH

FFO

OHCF3

FH

FF


C-H 95.7100.7103.5103.4100.9101.199.8106.0101.1102.099.595.398.9104.099.6100.798.693.797.5102.998.9100.997.593.797.3102.698.6101.097.294.197.5102.8101.0101.3104.8102.3102.6104.5102.0103.2

97.497.9102.8100.0100.7103.599.7103.4100.9

Chandra, A. K.; Uchimaru, T.; Urata, S.; Sugie, M.; Sekiya, A. J. Chem. Kinetics 2003, 35(3) , 130-138

CF3OCHF2

CHF2OCHF2

CF3CF2OCH3

CF3CF2CF2OCH3

(CF3)2CFOCH3

CF3CH3

CF3CH2F

CF3CHF2

CF3CH2Cl

CF3CHCl2CF3CHFCl

CF2ClCH3

CF2ClCH2F

CF2ClCHF2

CF2ClCH2Cl

CF2ClCHCl2CF2ClCHFCl

CFCl2CH3

CFCl2CH2F

CFCl2CHF2

CFCl2CH2Cl

CFCl2CHCl2CFCl2CHFCl

CCl3CH3

CCl3CH2F

CCl3CHF2

CCl3CH2Cl

CCl3CHCl2CCl3CHFCl

CHF2CHF2

CF3CHFCF3

CF3CH2CHF2

CF3CH2CHF2

CF3CH2CH2CF3

CF3CH2CF2CH3

CF3CH2CF2CH3

CHF2CF2CF2CHF2

CF3CF2CH2CH2CF2CF3

CH3OCH2F

CH3OCH2F

CH3OCHF2

CH3OCHF2

CF3OCH3

CF3OCHF2

CH2FOCH2F

CHF2OCHF2

CF3CF2OCH3

CH3OCH3

CF3OCH3


C-H 101.199.8101.8100.5103.9101.599.5102.3100.7100.696.9103.998.498.8100.699.1103.898.3103.7


α −Napthalene C-H 111.2110.7 B3LYP/6-31+G(d)

β −Napthalene 111.9110.6 B3LYP/6-31+G(d)

Reed, D. R.; Kass, S. R. J. Mass Spectrom . 2000, 35 , 534–539

C-H 106.0101.1102.099.595.398.993.797.597.3102.6

95.7100.7


CF3 CH3

F3C CH2F

F3C CHF2

F3C CH2Cl

F3C CHCl2F3C CHFCl

CF2Cl CHCl2CF2Cl CHFCl

CFCl2 CHFCl

CCl3 CH3

CH3OCH3

CF3OCH3

CF3CF2CF2OCH3

(CF3)2CFOCH3

CH3OCF2CHF2

CH3OCF2CHF2

CH2FCF2OCHF2

CH2FCF2OCHF2

CHF2CF2OCH2CF3

CHF2CF2OCH2CF3

CF3CHFCF2OCH3

CF3CHFCF2OCH3

CF3CH2OCH2CF3

CF3CF2CH2OCHF2

CF3CF2CH2OCHF2

CHFClCF2OCH3

CHFClCF2OCH3

CHF2OCF2CHFCl

CHF2OCF2CHFCl

CHF2OCHClCF3

CHF2OCHClCF3


C-H homolytic 87

86.5

85

87

85

87

85.5

86

86

87

87

89

J . Org. Chem . 1995, 60 , 6348-6352 Reference includes radical anion dissociation energies

O2NH

NO2

H

NO2

HO2N

NO2

MeH3CO H

NO2

MeH

H3CO

NO2

MeH

NO2

MeHF

NO2

MeH

O2N

NO2

MeHO2N

NO2

MeH

O2N

O2N

MeNO2

H

NO2

MeHMe


C-H (OoK) 35.6 CBS-4298oK 36.3 CBS-4

Experimental 35.2OoK 35.6 CBS-4

298oK 36.4 CBS-4Experimental 35.0

OoK 35.6 CBS-4298oK 36.3 CBS-4

Experimental 34.9

OoK 35.4 CBS-4298oK 36.2 CBS-4

Experimental 34.9

OoK 35.4 CBS-4298oK 36.2 CBS-4

Experimental 33.3

OoK 32.3 CBS-4298oK 33.2 CBS-4

Experimental 31.9

OoK 32.6 CBS-4298oK 33.4 CBS-4

Experimental 32.0

OoK 29.8 CBS-4298oK 30.8 CBS-4

Experimental 29.7

OoK cis 34.1 CBS-4trans 32.5 CBS-4

298oK cis 35.0 CBS-4trans 33.5 CBS-4

Experimental cis 33.2trans 32.2

OoK 33.9 CBS-4298oK 35.0 CBS-4

Experimental 34.0

OoK 33.1 CBS-4298oK 34.2 CBS-4

Experimental 32.5

OoK 48.1 CBS-4298oK 49.2 CBS-4

Experimental 47.6Zhang, X.-M.J. Org. Chem. 1998, 63, 1872-1877

H2CH

MeH

Me

H

CH2

Me

H

Me

CH2

H

H

Me

Me H

Me

MeMe H

Me

Me CH2

H

H

MeMe

Me

MeH

H

H


C-H (OoK) 47.7 CBS-4298oK 48.5 CBS-4

Experimental 47.5

OoK 45.2 CBS-4298oK 46.4 CBS-4



OoK cis 45.7 CBS-4trans 44.8 CBS-4

298oK cis 46.9 CBS-4trans 46.0 CBS-4

Experimental cis 45.5trans 44.3

OoK 44.6 CBS-4298oK 45.6 CBS-4

Experimental 45.8

OoK 49.4 CBS-4298oK 50.6 CBS-4

Experimental 49.3

OoK 44.6 CBS-4298oK 45.5 CBS-4

Experimental 47.5

OoK 44.3 CBS-4298oK 45.2 CBS-4

OoK 29.7 CBS-4298oK 30.5 CBS-4

Experimental 32.5

OoK 109.0 CBS-4298oK 110.6 CBS-4

Experimental 110

OoK 37.9 CBS-4298oK 39.1 CBS-4

Experimental 35.6

OoK 105.8 CBS-4298oK 107.4 CBS-4

OoK 35.0 CBS-4298oK 36.1 CBS-4

Experimental 36.2Zhang, X.-M.J. Org. Chem. 1998, 63 , 1872-1877

H

CH2

H

Me H

H

H

H

Me

Me

H

H

H

Me

H

MeH

H

Me

Me

H


C-H (OoK) 110.0 CBS-4298oK 111.5 CBS-4OoK 30.7 CBS-4


OoK 109.6 CBS-4298oK 111.1 CBS-4

OoK 31.1 CBS-4298oK 32.3 CBS-4

Experimental 32.5

OoK 57.2 CBS-4298oK 58.6 CBS-4



OoK 53.5 CBS-4298oK 54.7 CBS-4

Zhang, X.-M.J. Org. Chem. 1998, 63 , 1872-1877

C-H 111.4 Experimental110.9 B3LYP/6-31G(d), 298K110.6 B3LYP/6-311++G(d,p), 298K

108.9 Experimental109.3 B3LYP/6-31G(d), 298K108.3 B3LYP/6-311++G(d,p), 298K

88.5 Experimental87.9 B3LYP/6-31G(d), 298K

88.1 Experimental85.1 B3LYP/6-31G(d), 298K84.1 B3LYP/6-311++G(d,p), 298K

van Scheppingen, W.; Dorrestijn, E.; Arends, I.; Mulder, P. J. Phys. Chem. A 1997, 101, 5404-5411

H

H H

Me

H H

Me

CH2

H

H

H

H

MeH

H

Me

H

Me

Me

HH

MeH


CH4 C-H 106.0 (RO) B3LYP118.9 (RO) B3PW86106.2 (RO) B3PW91102.3 (RO) PW91LYP105.1 B3LYP 6-311G(d,p)105.5 (RO)B3LYP 6-311++G(3df,2p)102.8 MP2/cc-pVtz104.9 Experimental

CH3F 100.6 (RO) B3LYP113.3 (RO) B3PW86100.7 (RO) B3PW9195.3 (RO) PW91LYP99.7 B3LYP 6-311G(d,p)101.1 (RO)B3LYP 6-311++G(3df,2p)99.7 MP2/cc-pVtz101.3 Experimental

CH2F2 100.3 (RO) B3LYP113.1 (RO) B3PW86100.4 (RO) B3PW9194.4 (RO) PW91LYP99.7 B3LYP 6-311G(d,p)100.7 (RO)B3LYP 6-311++G(3df,2p)100.0 MP2/cc-pVtz103.2 Experimental

CHF3 104.9 B3LYP 6-311G(d,p)105.4 (RO)B3LYP 6-311G(d,p)105.3 (RO)B3LYP 6-311++G(3df,2p)105.1 MP2/cc-pVtz106.7 Experimental

CH3Cl 100.6 (RO) B3LYP113.1 (RO) B3PW86100.6 (RO) B3PW9195.7 (RO) PW91LYP99.6 B3LYP 6-311G(d,p)99.5 (RO)B3LYP 6-311++G(3df,2p)97.7 MP2/cc-pVtz100.1 Experimental

CHCl3 93.1 B3LYP 6-311G(d,p)93.9 (RO)B3LYP 6-311G(d,p)92.1 (RO)B3LYP 6-311++G(3df,2p)93.2 MP2/cc-pVtz93.8 Experimental

Chandra, A. K.; Uchimaru, T. J. Phys. Chem. A 2000, 104, 9244-9249


CH2Cl2 C-H 96.9 (RO) B3LYP109.3 (RO) B3PW8696.8 (RO) B3PW9191.6 (RO) PW91LYP96.0 B3LYP 6-311G(d,p)95.4 (RO)B3LYP 6-311++G(3df,2p)93.8 MP2/cc-pVtz96.2 Experimental

CH2FCl 98.2 B3LYP 6-311G(d,p)99.0 (RO)B3LYP 6-311G(d,p)98.4 (RO)B3LYP 6-311++G(3df,2p)100.8 Experimental

CHF2Cl 100.5 B3LYP 6-311G(d,p)101.1 (RO)B3LYP 6-311G(d,p)100.4 (RO)B3LYP 6-311++G(3df,2p)100.7 Experimental

CHFCl2 96.8 B3LYP 6-311G(d,p)97.5 (RO)B3LYP 6-311G(d,p)96.2 (RO)B3LYP 6-311++G(3df,2p)98.9 Experimental

CH3Br 100.2 B3LYP 6-311G(d,p)101.2 (RO)B3LYP 6-311G(d,p)100.9 (RO)B3LYP 6-311++G(3df,2p)98.9 MP2/cc-pVtz101.6 Experimental

CH2Br2 96.1 B3LYP 6-311G(d,p)97.0 (RO)B3LYP 6-311G(d,p)96.8 (RO)B3LYP 6-311++G(3df,2p)96.3 MP2/cc-pVtz99.7 Experimental

CHBr3 91.7 B3LYP 6-311G(d,p)92.6 (RO)B3LYP 6-311G(d,p)92.4 (RO)B3LYP 6-311++G(3df,2p)93.2 MP2/cc-pVtz96.0 Experimental

CH2FBr 98.1 B3LYP 6-311G(d,p)98.8 (RO)B3LYP 6-311G(d,p)98.5 (RO)B3LYP 6-311++G(3df,2p)



CHF2Br C-H 98.9 B3LYP 6-311G(d,p)99.5 (RO)B3LYP 6-311G(d,p)99.1 (RO)B3LYP 6-311++G(3df,2p)

CHFBr2 94.9 B3LYP 6-311G(d,p)95.6 (RO)B3LYP 6-311G(d,p)94.6 (RO)B3LYP 6-311++G(3df,2p)

CH2ClBr 96.1 B3LYP 6-311G(d,p)97.0 (RO)B3LYP 6-311G(d,p)96.2 (RO)B3LYP 6-311++G(3df,2p)

CHCl2Br 92.6 B3LYP 6-311G(d,p)93.4 (RO)B3LYP 6-311G(d,p)92.2 (RO)B3LYP 6-311++G(3df,2p)

CHBr2Cl 92.2 B3LYP 6-311G(d,p)93.0 (RO)B3LYP 6-311G(d,p)92.2 (RO)B3LYP 6-311++G(3df,2p)

CHFClBr 95.8 B3LYP 6-311G(d,p)96.6 (RO)B3LYP 6-311G(d,p)95.9 (RO)B3LYP 6-311++G(3df,2p)

HOH 114.2 B3LYP 6-311G(d,p)115.1 (RO)B3LYP 6-311G(d,p)118.4 (RO)B3LYP 6-311++G(3df,2p)119.0 Experimental


C-H 106.0 (RO)B3LYP 6-311G(d,p)105.8 (RO)B3LYP 6-311++G(3df,2p)106.7 Experimental

101.1 (RO)B3LYP 6-311G(d,p)101.1 (RO)B3LYP 6-311++G(3df,2p)

102.0 (RO)B3LYP 6-311G(d,p)101.7 (RO)B3LYP 6-311++G(3df,2p)102.7 Experimental





F3C CH3

F3C CH2F

F3C CH2Cl

F3C CHF2

F3C CHCl2

F3C CHFCl


C-H 104.0 (RO)B3LYP 6-311G(d,p)103.8 (RO)B3LYP 6-311++G(3df,2p)



















CF2Cl CH3

CF2Cl CH2F

CF2Cl CHF2

CF2Cl CH2Cl

CF2Cl CHCl2

CF2Cl CHFCl

CFCl2 CH3

CFCl2 CH2F

CFCl2 CHF2

CFCl2 CH2Cl

CFCl2 CHCl2

CFCl2 CHFCl

CCl3 CH3

CCl3 CH2F

CCl3 CHF2

CCl3 CH2Cl

CCl3 CHCl2

CCl3 CHFCl


C-H 102.8 corrected MP2/cc-pVtz103.8 CCSD(T)/6-311++G(3df,3pd)105.1 Experimental

99.7 corrected MP2/cc-pVtz98.5 CCSD(T)/6-311++G(3df,3pd)101.3 Experimental



100.0 corrected MP2/cc-pVtz101.3 Experimental





93.2 corrected MP2/cc-pVtz96 Experimental

McGivern, W. S.; D.-K., A.; North, S. W.; Francisco, J. S. J. Phys. Chem. A 2000, 104, 436-442

Tp'Rh(CNneo)(R)H R = Ph C-H 113.5

R = 109.7

R = Me 104.9R = n -pentyl 98

R = cyclopentyl 96.4

R = cyclohexyl 96

R = Mesityl 88.5

R = Methallyl 85.6

Wick, D. D.; Jones, W. D. Organometallics 1999, 18, 495-505

CH2F H

CH2Cl H

CH2Br H

CH3 H

CHF2 H

CHCl2 H

CHBr2 H

CF3 H

CCl3 H

CBr3 H

tBu

H

Me

Me

Me

Me Me

MeMe


Re(Cp)(CO)2(H)(R) R = Ph C-Re 252.0 All calculated withC-H 489.8 B3PW91 (Hybrid DFT)

R = C-Re 276.9C-H 500.5

R = C-Re 253.5C-H 490.6

R = C-Re 255.3C-H 494.3

R = C-Re 300.0C-H 512.0

R = C-Re 278.7C-H 501.2

R = C-Re 278.1C-H 500.3

R = C-Re 279.9C-H 504.6

R = C-Re 255.4C-H 492.0

R = C-Re 256.1C-H 494.5

R = C-Re 301.2C-H 511.8

R = C-Re 302.7C-H 515.5

R = C-Re 280.4C-H 501.7

Clot, E.; Besora, M.; Maseras, F.; Megret, C.; Eisenstein, O.; Oelckers, B.; Perutz, R. N. Chem. Commun. 2003, 490-491

F

LnRe

LnRe

F

LnRe F

LnRe

F

F

LnRe

F

F

LnRe

F F

LnRe

F

F

LnRe

F

F

LnRe

F

F

LnRe

F F

F

LnRe

F

F

F

LnRe

F F

F

Compound Bond Dissociation Enthalpy (kJ/mol)Bond (C-Y) Energy Theory Level

Re(Cp)(CO)2(H)(R) R = C-Re 280.8 All calculated withC-H 503.6 B3PW91 (Hybrid DFT)

R = C-Re 281.0C-H 504.8

R = C-Re 257.4C-H 495.0

R = C-Re 304.7C-H 512.4

R = C-Re 304.0C-H 514.7

R = C-Re 283.0C-H 504.4

R = C-Re 306.7C-H 514.7

Clot, E.; Besora, M.; Maseras, F.; Megret, C.; Eisenstein, O.; Oelckers, B.; Perutz, R. N. Chem. Commun. 2003, 490-491(kcal/mol)

RSE 6.3 C-H 92.4

Brocks, J. J.; Welle, F. M.; Beckhaus, H.-D.; Rüchardt, C. Tet. Lett. 1997, 38(44) , 7721-7724

N

N

N

N

O

O

O

O

Me

Me

Me

Me

H

LnRe

F

F

F

LnRe F

F

F

LnRe

F

FF

F

LnRe

FF

F

F

LnRe

FF

F

F

LnRe

FF

F

FF

LnRe

F F

F

Compound Bond Dissociation Enthalpy (kcal/mol)Bond (C-Y) Energy Solvent

C-H 77 isooctane

93 isooctane

92 water

92 water

89 water

90 water

(CH2(-H))3OH 99 water

96 water

92 water

78 benzene

77 benzene

Laarhoven, L. J. J.; Mulder, P.; Wayner, D. D. M. Acc. Chem. Res . 1999, 32, 342-349

OMe

HMe

C OHH

HH

OHMe

MeH

OH

HO

H

CNH

H H

COO-

H

H H

H

MeMe

H

MeOH

H

Me

H

Compound Bond Dissociation Enthalpy (kcal/mol)Bond (C-Y) Energy Solvent

C-H 77 benzene

77 benzene

69 benzene

78 benzene

94 benzene

93 benzene

92 THF

83 tetralin

Laarhoven, L. J. J.; Mulder, P.; Wayner, D. D. M. Acc. Chem. Res . 1999, 32, 342-349

C-H 104.9101.1

98.6

96.5

110.7

88.8

112.9

89.7

104.6

88.1

89.4

Blanksby, S. J.; Ellison, G. B. Acc. Chem. Res. 2003, 36 , 255

H

H Me

H OH

O

HN

O

H

O

HNH

NH

HNH

OH

H

H CH3

MeH

Me

MeH

Me Me

H

H H

HH

H

H

H OMe

O

HHO

HMe

HMe


C-H 104.99110.4101.3126.380.9101.1

98.6

98.2

96.5

110.7

133.32

112.9

78

94

109

88.8

89.8


H CN

H CH3

H CH2

H CH

H C

HMe

HMe

MeH

HEt

MeH

HMe

MeMe

HH

H H

HH

H

H

H

H

H

H

HH


C-H 101.1

110.7

35.7

83

35.4

133.32

86

112.9

78

94

109


C-H 96.1

22.0

105

88.0

-12


H

HH

H

HH

H

HH

H

H

H

OH

C OH

H

OH

H

MeH

H2CH

HH

H

H

H

H

OHH

HO

O

Compound Resultant Bond Dissociation Enthalpy (kJ/mol)Radical Bond (C-Y) Energy Bond Enthalpy Terms (E )

CH C-H 341HCH 426HCH2 458HCH3 439.4C2H 485C2H2 555C2H4 461C2H6 421 410.8C3H6 363 410.8C3H8 Pr 418 410.8

i -Pr 406 407.0C4H10 Bu 418 410.8

s -Bu 406 407.0Me3CH i -Bu 420 410.8

t -Bu 396 403.9CpH 347

c -C5H10 395C5H12 418 410.8

Me3CCH3 418 410.8C6H6 465 420.6

c -C6H12 400 407.02,3-Me2C4H8 2,3-Me2Bu 418 410.8

PhCH3 Bz 368 410.8MeC6H4 465 420.6

PhCCH 553 435PhCH2Me 357 407.0c -C5Me5 368

Simões, J.A.M.; Beauchamp, J.L. Chem. Rev. 1990, 90 , 629-688

C-H 381 Experimental379.5 Estimated

381 Experimental370.2 Estimated

438.56Cherkasov, A.; Jonsson, M. J. Chem. Inf. Comput. Sci. 2000, 40, 1222-1226

N

Me

Me

Me

H

N

Bu

BuEt

H

H3C H

Compound Resultant Bond Dissociation Enthalpy (kJ/mol)Radical Bond (C-Y) Energy Bond Enthalpy Terms (E )

BuCH2OH C-H 389 401.7PhOH 362 451.2

PhC(O)H 371 426.6CF2H 274CF3H 447 420CH2F 359CH3F 424CH2F2 430

CF3C(O)H 381 426.6CF3CH2OH 436 451.2

C6F5OH 362 451.2HCl 432.0HBr 366.3HI 298.4

SiH3 304SiMe4 415HCO H 63

MeCO Me 61EtCO Et 49PrCO Pr 46PhCO Ph 104Me2CO MeCO 340

MeC(O)Cl MeCO 340PhC(O)Cl PhCO 343

MeI 238C2H3I C2H3 272

EtI 235C3H5I C3H5 180

PrI 235i -PrI 232BuI 237PhI 273BzI 207

PhCH2CH2I 237Me(CHEt)2

- 237PhCCI 319

Me3SiCH2I 232I2 151.3

PhC(O)I 212MeC(O)I MeCO 209

Simões, J.A.M.; Beauchamp, J.L. Chem. Rev. 1990, 90 , 629-688


CH4 C-H 421.1 B3LYP427.4 KMLYP439.5 CBS-Q438.9 Experimental

411.6 B3LYP419.3 KMLYP425.5 CBS-Q420.7 Experimental






458.2 B3LYP468.9 KMLYP471.7 CBS-Q

436.3 B3LYP447.7 KMLYP452.1 CBS-Q


Senosiain, J. P.; Han, J. H.; Musgrave, C. B.; Golden, D. M. Faraday Discuss. 2001, 119 , 173-189Reference includes radical stabilization energies

H

H

H

Me

MeH

Me

H

H

Me

H

Me

H

MeH


C-H 562.2 B3LYP570.2 KMLYP566.1 CBS-Q







413.8 B3LYP422.2 KMLYP471.2 CBS-Q

415.4 B3LYP424.6 KMLYP427.9 CBS-Q

333.9 B3LYP343.3 KMLYP347.9 CBS-Q


H Me

H

H

H

Me

H

MeMe

MeMe

Me

H

H

Me

Me

H

H

Me

H

Me


C-H 348.1 B3LYP357.3 KMLYP360.5 CBS-Q358.2 Experimental

447.3 B3LYP459.4 KMLYP

402.1 B3LYP414.2 KMLYP408.8 CBS-Q

462.5 B3LYP471.7 KMLYP468.3 CBS-Q



421.1 B3LYP429.7 KMLYP427.5 CBS-Q




366.2 B3LYP373.8 KMLYP376.2 CBS-Q


H

Me

H

Me

H

H

H Me

HMe

H

Me

H

H

H

H


C-H 459.0 B3LYP472.7 KMLYP467.5 CBS-Q

460.5 B3LYP472.8 KMLYP474.0 CBS-Q

413.9 B3LYP415.9 KMLYP428.3 CBS-Q



386.6 B3LYP400.1 KMLYP404.0 Experimental









H

H

H

MeMe

H

MeMe Me

H

Me

H

Me

H

Me

H

H

H

Me

MeMe

H

MeMe

H

MeMe

H

Me


C-H 335.4 B3LYP350.2 KMLYP338.9 Experimental




389.2 B3LYP389.6 KMLYP406.4 CBS-Q









H

MeH

Me

H

H

H

H

H

H

H

H

H

H

Me Me

MeH





Senosiain, J. P.; Han, J. H.; Musgrave, C. B.; Golden, D. M. Faraday Discuss. 2001, 119 , 173-189Reference includes radical stabilization energies (kJ/mol)

C-H 438.9 Experimental429.7 Estimated




412.5 Experimental411.6 Estimated









Cherkasov, A.; Jonsson, M. J. Chem. Inf. Comput. Sci. 2000, 40, 1222-1226

H

H

H

MeH

H

MeH

HMe

Me

H

H

Me

HMe

Me

HMe

MeMe

NCH

Me NHH

Me NH

Me

CH3H

MeH

Me



















HO

H

Me

H

H

MeMe

NCH

Me

NCMe

MeH

HSH

Me SH

F3C H

H

Me

HH

H

HMe

H

H

MeMe

H



















HMe

MeH

MeMe H

H

Me

MeMe

H

Me

Me

MeH

MeMe

MeH

Me

Me

Me

H

Me

MeMe

H

H

HMe

O

MeH

Me OH

O

MeH

Me

OH

Me

Me

HHO

HHO

Me


C-H 381 Experimental382.6 Estimated

















HHO

Me Me

HF

H H

HF

F H

HF

Cl H

HF

F Cl

HF

Cl Cl

HH

Cl H

HCl

Cl H

HCl

Cl Cl

HBr

H H

HBr

Br H

HBr

Br Br

HI

H H

HI

I H

HMe

F F

HF3C

F F



















HF3C

Cl H

H

ClCl

H

ClCl

H

ClCl

Cl

ClCl

H

ClBr

F

FF

HF F

FF

F

FF

FF F

HF

F

FF

SiMe

MeMe

H

O

Me H

Me

O

HOH

H2NH

H2NH

MeMe

H2NH

Me

NH

H

NH

HN

H

NH

O

H

HN H


C-H 416.6 ab-initio422.6 Experimental

370.7 ab-initio375.9 Experimental




426 ab-initio



407.3 ab-initio





Seetula, J. A. J. Chem. Soc Faraday Trans. 1998, 94 , 891-898

H3CH

H3C CH3

Cl

H

MeH

Cl

H3CCl

H

Cl

Cl

CH3

Cl

Cl

Cl

Cl

H

Cl

Cl

MeH

HMe

Me

MeCH3

MeH

ClCl


C-H 418.7 ab-initio






420.0 ab-initio

401.5 ab-initio



Seetula, J. A. J. Chem. Soc Faraday Trans. 1998, 94 , 891-898

C-H 357

453.5

359.9 ± 20

Ling, Y.; Lifshitz, C. J. Mass Spec. 1997, 32 , 1219-1225

Cl

H

Cl

H

Me

MeH

Cl

MeCl

H3CCl

MeH

Cl

HCl

Me Me

ClMe

Me

H3CCl

Me

H

H

H

MeCl


C-H 112.3 DFT-AM1102.0, 102.2 Experimental

108.0 DFT-AM198.0, 98.3 Experimental















Jursic, B. S. J. Chem. Soc. Perkin Trans. 1999, 2 , 369-372

H3C H

HMe

MeMe

H

H

H

NCH

H

H

H

H

H

H

H

HMe

HMe

Me

HH


C-H 133.0 DFT-AM1120.0, 121.0 Experimental




Jursic, B. S. J. Chem. Soc. Perkin Trans. 1999, 2 , 369-372

C-H 83.3 Calculated85.6 Experimental

79.9 Calculated78.9 Experimental

88.3 Calculated

84.6 Calculated86.6 Experimental

Glasovac, Z.; Eckert-Maksic, M.; Dacres, J. E.; Kass, S. R. J. Chem. Soc. Perkin Trans. 2 2002, 2 , 410-415

C-H 79.4 HF100.3 MP2105.8 B3LYP

104.7, 104.9 Experimental

76.8 HF98.9 MP2101.1 B3LYP


74.5 HF95.3 MP297.1 B3LYP


72.7 HF93.7 MP294.0 B3LYP


77.8 HF96.0 MP299.1 B3LYP101.7 Experimental Avg

Korth, H.-G.; Sicking, W. J. Chem. Soc. Perkin Trans. 2 1997, 715-719

NC H

HO

Me OH

H

H

H

H

H3C H

HMe

Me

HMe

Me Me

FH2C H

HO

Me

MeH


C-H 76.6 HF95.0 MP299.7 B3LYP101.5 Experimental Avg

74.1 HF92.3 MP295.2 B3LYP




69.8 HF96.2 MP293.8 B3LYP

92.6, 94.8, (93.4) Experimental (Avg)






Korth, H.-G.; Sicking, W. J. Chem. Soc. Perkin Trans. 2 1997, 715-719

ClH2C H

HHO

HH2N

HHS

HNC

HMe

O

Me

O

H

O

HOH

S

O

O

MeH

Cl3C H


C-H 106.6 MP2/cc-pVtz (298K)106.7 Experimental

94.7 MP2/cc-pVtz (298K)95.8 Experimental

93.2 MP2/cc-pVtz (298K)96 Experimental








McGivern, S. W.; Derecskei-Kovacs, A.; North, S. W.; Francisco, J. S. J. Phys Chem. A, 2000, 104 , 436(kJ/mol)

Polycyclic Aromatic Hydrocarbon Borders C-H

Zigzag border ~480Armchair border ~477Second Armchair dissociation ~361May, K.; Dapprich, S.; Furche, F.; Unterreiner, B. V.; Ahlrichs, R. Phys. Chem. Chem. Phys. 2000, 2 , 5084-5088

(kcal/mol)C-H 84.8, 85.7 DFT

87 Experimental

92.1 DFT96 Experimental

71.4, 72.3 DFT77 Experimental


Kranenburg, M.; Ciriano, M. V.; Cherkasov, A.; Mulder, P. J. Phys. Chem. A 2000, 104 , 915-921

F3C H

Cl3C H

Br3C H

H3C H

FH2C H

ClH2C H

BrH2C H

F2HC H

Cl2HC H

Br2HC H

c-C6H7 H

H

H

Me

Cl3C H


C-H 97 Photoacoustic Calorimetry

77 Photoacoustic Calorimetry

88.2, (87) DFT, (Expt)

89.9, 89 DFT, (Expt)

90.7, 91.6, (92) DFT, (Expt)

94.6, (96) DFT, (Expt)






106.4, 107.2 DFT

97.3, 98.0 DFT



105.7 DFT




Kranenburg, M.; Ciriano, M. V.; Cherkasov, A.; Mulder, P. J. Phys. Chem. A 2000, 104 , 915-921

c-C6H11

c-C6H7

c-C4H8N

N(Et)2CHCH3

C4H7O

C4H7O2

H3C H

C2H5 H

C3H7 H

MeMe

H

MeMe

H

c-C3H5 H

c-C4H7 H

c-C6H11 H

C2H3 H

Me

H

H

H

HMe


C-H91.3 ALL ab-initio

91.5

91.5

91.6

91.8

92.0

92.0

92.2

92.2

88.4 G3

89.4 G389.3 Experimental

91.2 G3

91.6 CBS-4M88.9 Experimental

Feng, Y.; Huang, H.; Liu, L.; Guo, Q.-X. Phys. Chem. Chem. Phys. 2003, 5 , 685-690

O

HH

O

HMe

O

HO

H

H2NO

H

HOO

H

MeO

H

HO

H

FO

H

HOOCO

H

F3CO

H

NCO

H

O2NO

H

Documents

Compound Bond Dissociation Enthalpy (kcal/mol) Bond (C-Y ...lectka.chemistry.jhu.edu/assets/Bond-Strength-Files/C-H-bond-str.pdfR = 4-CH 3OPh heterolysis 66.9 homolysis 69.4 R = 4-CH