8_Bond Dissociation Enthalpy Data

The Lectka Group at Johns Hopkins University

Bond Dissociation Enthalpy Data

http://www.jhu.edu/chem/lectka/Extras.html

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

C-CN 122.4

121.6

120.9

117.8

133

108.7

134Blanksby, S. J.; Ellison, G. B. Acc. Chem. Res. 2003, 36 , 255

C-CN111.4

110.6

110.5

110.1

110.0

109.7

109.6

109.4

109.1

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

H2NO

CN

HOO

CN

H3CO

CN

HO

CN

FO

CN

HOOCO

CN

F3CO

CN

NCO

CN

O2NO

CN

NC CH3

MeNC

Me

MeNC

Me Me

NC

NC

CN

NCCH3


C-CN104.7 G3

107.3 G3

108.9 G3

110.1 CBS-4M

83.5 G3

83.4 G384.4 Experimental

84.1 G3

86.4 CBS-4M


Polycyclic Aromatic Hydrocarbon BordersZigzag border C-CH3 ~428Armchair border ~394Second Armchair dissociation ~287May, K.; Dapprich, S.; Furche, F.; Unterreiner, B. V.; Ahlrichs, R. Phys. Chem. Chem. Phys. 2000, 2 , 5084-5088

C-C 91.3 G291.5 G2MP292.3 G2MS

90.3 G290.6 G2MP291.2 G2MS

97.0 G2MP297.2 G2MS

94.4 G2MP294.7 G2MS

97.8 G2MP298.0 G2MS

Fukaya, H.; Ono, T.; Abe, T. J. Phys. Chem. A 2001, 105 , 7401-7404

O

CNH

O

CNMe

O

CNO

CN

O

CH3H

O

CH3Me

O

CH3

O

CH3

H3CMe

F3CCF3

F

MeMe

F3CCF3

F F

FF

F3CCF3

F F

FF


C-C 89.36 ab-inito87.0 Experimental87.88 0 K89.41 Equilibrium Distance D e

93.85 ab-inito92.36 0 K93.68 Equilibrium Distance D e


100.91 ab-inito101 Experimental

99.42 0 K100.58 Equilibrium Distance D e






96.20 ab-inito98.7, 97.27 Experimental

94.27 0 K96.73 Equilibrium Distance D e

Olleta, A. C.; Lane, S. I. Phys. Chem. Chem. Phys. 2001, 3 , 811-818

CFCl2 CH3

CF2Cl CH3

CF3 CH3

CF3 CClH2

CF3 CCl2H

CF3 CCl3

CF3 CCl2F

CF3 CClF2

CF3 CF3

CCl3 CH3


C-C 95.2 DFT-AM188.0 Experimental86.6 Corrected

102.3 DFT-AM1101.2 Experimental93.1 Corrected











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

CH3 CH3

CH3 CF3

CF3 CF3

CF3 CN

CN CN

Me

H3CCN

NH2

O

Me

O

Me

O

OH

O

O

CF3


C-C 376.5 ab-initio371.4 Experimental

378.2 ab-initio370.4 Experimental







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

C-C91

78.7

142.4178.2230.7

165

99.4

174.1

90.1

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

H3CCl

H3CCl

H3CCl

Me

H3CCH3

Cl

Cl

CH3

Cl

Cl

H3CCl

H3C CH3

C OH

C OH

H

HH

H

H2CH

H

HH

H

HHH

H3C CH3


C-Ph 103.5

102.2

101.0

98.3

116

118

97

101

99.3

98.8

77.6

76.7

76.4

65.2

71.4


C-C 89.0

87.9

125.1


CH3

CH3

OMe

O

H

O

Me

CH3

Me

MeMe

O

Me

Me

MeMe

H

HMe

H3CMe

Me

MeMe

MeMe


C-CHCH2 101.4

100.0

99.2

97.8

116

87.3

116

41


C-CH2CHCH2 76.5

75.4

75.2

73.2

87.3

62.7


C-CCH 126.5125.1

124.5

122.3

78


H3C

Me

Me

MeMe

MeMe

CH3H

HMe

Me

HMe

MeMe

HMe

HMe

H3C

Me

MeMe

MeMeMe

O

Me

HMe


C-C(CH3)3 87.5

85.6

82.7

78.6

97.8

73.2

98.3

84

79.4


C-CH3 90.189.0

88.6

87.5

101.476.5

103.5

77.6

83.2

84.8

84.5


MeMe Me

Me

MeMe

MeMe

Me

MeMe

MeMe

Me

Me

MeMeMe

Me

MeMe

Me

MeMe

MeMeO

Me Me

O

MeMe

MeMe

H3C CH3

MeH3C

Me

MeH3C

Me Me

H3C

H3C

CH3

H3C OMeO

CH3HO

CH3Me

MeH3C

Me Me

CH3

H3CMe


C-CH3 85.5

86.1

86.2

86.4

86.5

87.1

87.2

87.4

87.6


C-CH2CH3 89.0

87.9

87.1

85.6

100.0

75.4

102.2

76.7

85

83.3

83.5Blanksby, S. J.; Ellison, G. B. Acc. Chem. Res. 2003, 36 , 255

H2NO

CH3

HOO

CH3

H3CO

CH3

HO

CH3

FO

CH3

HOOCO

CH3

F3CO

CH3

NCO

CH3

O2NO

CH3

Me

Me

MeMe

Me

MeMe Me

MeMe

Me

O

HMe

O

MeMe

Me

H3CMe

Me

MeOMe


C-CH(CH3)2 88.6

87.1

85.6

82.7

99.2

75.2

101.0

76.4

85.8

83.1

81.9


C-C 87.8 Experimental

85.1 Experimental82.8 B3LYP/6-31G(d), 298K


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

MeMe

Me

MeMe

MeMe

MeMe

MeMe

Me

MeMe

Me

MeMe

Me

MeMe

MeMeO

Me

O

HMe

MeO

MeMe

Me

MeH3C

Me

Me


C-C 89.68

172.2

229.9

16.6

44.0

43.7

44.7

51.0

57.8

62.2

60.2

66.6

70.1

76.0

86.6

88.3

Zavitsas, A. A. J. Phys. Chem. A 2003, 107, 897-898 Reference includes bond distances in Angstroms

H3C CH3

Ph

Ph Ph

PhPhPh

Me

Me Me

Met-But-Bu

HH

H

H H

H

Me

MeMe

Me

Ph

Ph

Et

Et Et

EtMeMe

Et

Et Et

Eti-Pri-Pr

Et

Et Et

Eti-Bui-Bu

Et

Et Et

EtEtEt

Et

Et Et

EtPhPh

Cl

ClClCl

ClCl

Me

MeMeMe

MeMe

Me

MeMe

Me

H3CCl

ClCl


C-C 86.0

88.9

87.2

97.4

97.5

102.1

102.3

99.7

100.9

103.9

99.6

111.9

118.0

116.9

115.8


H3CMe

MeMe

H3CMe

Me

Me

MeMe

Ph

Me

MeMe

HH

H

Me

MePh

Me

PhMe

MeHH

H

CH3H

H

H

CH3

Me

HH

H

Me

MeMeN

Me

Me


C-C 121.1

116.0

123.5

132.7

132.1

140.7

133.6

155.0

152.4


C-C 66.10 HF and NR66.06 HF and RESC86.06 B3LYP and NR86.04 B3LYP and RESC81.77 BOP and NR81.76 BOP and RESC

Lie, W.; Fedorov, D. G.; Hirao, K. J. Phys. Chem. A 2002, 106, 7057-7061

CH3N

HH

HH

H

H

N

HH

HN

CH3Me

Me

CH3H

H

HH

HH

H H

NH


C-C 84.3 B3LYP85.9 B3PW9186.4 MPW1PW9188.6 B3P8688.1 CCSD(T)87.4 G2MSr90.4 Experimental

81.4 B3LYP83.0 B3PW9183.8 MPW1PW9185.7 B3P8687.4 CCSD(T)87.0 G2MSr85.8 Experimental

96.5 B3LYP97.9 B3PW9198.8 MPW1PW91100.8 B3P86101.8 Experimental



66.4 B3LYP68.5 B3PW9169.7 MPW1PW9171.2 B3P8678.1 G2MSr74.6 Experimental

Yao, X.-Q.; Hou, X.-J.; Wu, G.-S.; Xu, Y.-Y.; Xiang, H.-W.; Jiao, H.; Li, Y.-W. J. Phys. Chem. A 2002, 106, 7184-7189

H3C CH3

CH3

CH3Me

CH3Me

Me

CH3Me

MeMe

CH3

Me


C-C 66.3 B3LYP68.6 B3PW9169.8 MPW1PW9171.2 B3P8671.8 Experimental




66.3, 63.0 B3LYP68.9, 65.5 B3PW9170.3, 67.2 MPW1PW9171.8, 68.9 B3P86

92.4 B3LYP93.9 B3PW9195.1 MPW1PW9196.9 B3P86



Yao, X.-Q.; Hou, X.-J.; Wu, G.-S.; Xu, Y.-Y.; Xiang, H.-W.; Jiao, H.; Li, Y.-W. J. Phys. Chem. A 2002, 106, 7184-7189Reference includes bond distances in Angstroms

Me

CH3

Me

CH3

Me

CH3Me

MeMe

Me


C-C 93.1 B3LYP94.6 B3PW9195.8 MPW1PW9197.6 B3P86

92.6 B3LYP94.2 B3PW9195.4 MPW1PW9197.2 B3P86

87.4 B3LYP89.4 B3PW9191.1 MPW1PW9192.9 B3P86

76.2 B3LYP78.6 B3PW9180.9 MPW1PW9182.9 B3P86

91.0 B3LYP92.7 B3PW9194.1 MPW1PW9195.9 B3P86

74.8 B3LYP77.1 B3PW9179.0 MPW1PW9180.3 B3P86

73.3 B3LYP76.0 B3PW9178.2 MPW1PW9179.5 B3P86


Me

Me

Me Me

MeMe


C-C 54.1 B3LYP57.1 B3PW9158.5 MPW1PW9159.5 B3P8661.4 Experimental

46.9 B3LYP49.9 B3PW9152.1 MPW1PW9152.9 B3P86


75.7 B3LYP78.0 B3PW9179.7 MPW1PW9179.7 B3P86


31.8 B3LYP35.4 B3PW9138.5 MPW1PW9139.5 B3P86



Me

Me

MeMe

Me

Me

Me

Compound ∆Go (kcal/mol)Heterolysis Bond (C-Y) Energy (Solvent)

C-C

R = 8.7 (DMSO)

R+ = 8.2 (DMSO)

R+ = 8.3 (DMSO)∆Ho

het 19.6

R+ = 8.2 (DMSO)9.3 (Sulfolane)







R = 5.9 (DMSO)

R = 5.5 (DMSO)∆Ho

het 11.9

Kitagawa, T.; Takeuchi, K. J. Phys. Org. Chem. 1998, 11 , 157-170

C

R

Cl

Br


C-C

R = 4.6 (DMSO)

R = 4.8 (DMSO)

R = 4.6 (DMSO)

R = 4.6 (DMSO)

R = <4 (DMSO)4.8 (CH3CN)5.7 (ClCH2CH2Cl)6.7 (CH2Cl2)6.6 (THF)

R = <4 (DMSO)

R+ = <4 (DMSO)

R+ = <4 (DMSO)

R+ = <4 (DMSO)


Me

Me

Me

Me

C

R

OMe


C-C ∆Go

R+ = 9.3 (DMSO, CS2)

R+ = 8.2 (DMSO, CS2)

R+ = 7.7 (DMSO, CS2)

R = 6.2 (DMSO, CS2)

R+ = <4 (DMSO, CS2)

R+ = <4 (DMSO, CS2)


Me


R1 = CPh3, R2 = COOMe C-R1 heterol. 25.81R3, R4 = H homolysis 16.08

R1 = CPh3, R2 = SO2Ph heterolysis 28.35R3, R4 = H homolysis 22.38

R1 = CPh3, R2 = SPh heterolysis 29.41R3 = H, R4 = Br homolysis 15.60

R1 = CPh3, R2 = SPh heterolysis 33.61R3, R4 = H homolysis 12.96

R1 = CPh3, R2 = Ph heterolysis 35.51R3, R4 = H homolysis 13.18

R1 = Xan, R2 = COOMe heterolysis 24.62R3, R4 = Br homolysis 26.03

R1 = Xan, R2 = COOMe heterolysis 27.33R3, R4 = H homolysis 22.53

R1 = Xan, R2 = SPh heterolysis 30.13R3 = H, R4 = Br homolysis 21.25

R1 = Xan, R2 = SPh heterolysis 33.03R3, R4 = H homolysis 20.69

R1 = TPCP, R2 = COOMe heterolysis 16.22R3, R4 = Br homolysis 39.70

R1 = TPCP, R2 = CN heterolysis 19.56R3, R4 = H homolysis 38.54

R1 = TPCP, R2 = COOMe heterolysis 20.62R3, R4 = H homolysis 37.89

R1 = TPCP, R2 = SO2Ph heterolysis 22.23R3, R4 = H homolysis 43.26

R1 = TPCP, R2 = SPh heterolysis 25.40R3 = H, R4 = Br homolysis 38.59

R1 = TPCP, R2 = SPh heterolysis 27.49R3, R4 = H homolysis 37.22

R1 = TPCP, R2 = Ph heterolysis 29.34R3, R4 = H homolysis 34.02

Arnett, E.M.; Venimadhavan, S. J . Am. Chem. Soc. 1991, 113 , 6967-6975

R1

R2

R3

R4


R1 = C7H7, R2 = CO2Me C-R1 heterol. 19.45R3, R4 = Br homolysis 27.20

R1 = C7H7, R2 = CO2Me heterolysis 24.89R3, R4 = H homolysis 26.44

R1 = C7H7, R2 = SO2Ph heterolysis 27.17R3, R4 = H homolysis 32.47

R1 = C7H7, R2 = SPh heterolysis 28.59R3 = H, R4 = Br homolysis 26.05

R1 = C7H7, R2 = SPh heterolysis 30.52R3, R4 = H homolysis 24.52

R1 = C7H7, R2 = Ph heterolysis 33.84R3, R4 = H homolysis 22.79

R1 = CPh3, R2 = COOMe heterolysis 19.76R3, R4 = Br homolysis 16.23

Arnett, E.M.; Venimadhavan, S. J . Am. Chem. Soc. 1991, 113 , 6967-6975(kJ/mol)

C-C 361.7Leal, J. P.; Marques, N.; Takats, J. J. Organomet. Chem. 2001, 632 , 209–214

R1

R2

R3

R4

C5H11C5H11


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


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


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


C-H 77 benzene

77 benzene

69 benzene

78 benzene

94 benzene

93 benzene

92 THF

83 tetralin


C-H 104.9101.1

98.6

96.5

110.7

88.8

112.9

89.7

104.6

88.1

89.4


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



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





426 ab-initio



407.3 ab-initio






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




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
















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





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)







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





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


91.2 G3

91.6 CBS-4M88.9 Experimental


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


C-X 107.1 CCSD(T)/6-322++G(3df,3pd)108.0 corrected MP2/cc-pVtz108.1 IB method109.2 Experimental

79.6 CCSD(T)/6-322++G(3df,3pd)81.4 corrected MP2/cc-pVtz80.0 IB method83.2 Experimental

65.8 CCSD(T)/6-322++G(3df,3pd)70.6 corrected MP2/cc-pVdz69.7 corrected MP2/cc-pVtz69.5 corrected MP2/cc-pVqz69.1 IB method70.9 Experimental


C-X 119.3 corrected MP2/cc-pVtz118.8 Experimental

C-H 100.0 corrected MP2/cc-pVtz101.3 Experimental









C-X 63.8 corrected MP2/cc-pVtz66 Experimental

C-H 93.2 corrected MP2/cc-pVtz96 Experimental


H3C F

H3C Cl

H3C Br

CH2F F

CHF2 H

CH2Cl Cl

CHCl2 H

CH2Br Br

CHBr2 H

CHF2 F

CF3 H

CHCl2 Cl

CCl3 H

CHBr2 Br

CBr3 H


C-Cl 352.5Leal, J. P.; Marques, N.; Takats, J. J. Organomet. Chem. 2001, 632 , 209–214

(kcal/mol) (solvent)C-X 87 benzene

61 various


C-X 11583.772.157.6

Blanksby, S. J.; Ellison, G. B. Acc. Chem. Res. 2003, 36 , 255(kJ/mol)

C-X 459.69350.7291.8


ClC5H11

Cl

O

Br

H3C FH3C Cl

H3C Br

H3C F

H3C Cl

H3C Br

IH3C


C-F 115

110.6

123.3

127.2

98.7

122.2


C-Cl 83.784.8

85.2

84.9

91.2

97.1

74


C-Br 72.1

72.4

73.9

72.6

80.8

5984

63

71.7


MeF

Me

F

F

O

FMe

MeCl

Me

MeCl

Me Me

Cl

Cl

O

ClMe

MeBr

Me

MeBr

Me Me

Cl

F

Br

Br

Br

Br

O

BrMe

BrCH3

ClCH3

H3C F

H3C Cl

H3C Br


C-I 57.656.9

57

55.6

45.6

67

51

53.8


C-X 109.7 MP2/cc-pVtz (298K)109.8 Experimental






Fluoroform 129.1 MP2/cc-pVtz (298K)127.6 Experimental

Chloroform 76.6 MP2/cc-pVtz (298K)78.4 Experimental

Bromoform 64.6 MP2/cc-pVtz (298K)66 Experimental

McGivern, S. W.; Derecskei-Kovacs, A.; North, S. W.; Francisco, J. S. J. Phys Chem. A, 2000, 104 , 436

ICH3

MeI

Me

MeI

Me Me

I

I

I

O

IMe

H3C F

H3C Cl

H3C Br

FH2C F

ClH2C Cl

BrH2C Br

F2HC F

Cl2HC Cl

Br2HC Br

IH3C


C-X 73.6 G274.0 G2MP273.8 G2MS70.0 Experimental

74.8 G275.1 G2MP274.8 G2MS70.6 Experimental


C-X 426.1, 461.9 LLM Method

354.9, 354.8 LLM Method

312.9, 313.4 LLM Method

451.5 Experimental473.7 LLM Method



231.4 Experimental

412.8 Experimental416.6, 417.1 LLM Method



187.8 Experimental

Verevkin, S. P.; Krashnykh, E. L.; Wright, J. S. Phys. Chem. Chem. Phys. 2003, 5 , 2605-2611

H3C Br

F3C Br

CH3 F

CH3 Cl

CH3 Br

F

Cl

Br

I

FH3C

ClH3C

BrH3C

IH3C


C-X 453.1 Experimental482.5 LLM Method



227.2 Experimental

425.1 LLM Method



176.1 Experimental

483.7 LLM Method



226.9 Experimental

434.0 LLM Method



176.0 Experimental

Verevkin, S. P.; Krashnykh, E. L.; Wright, J. S. Phys. Chem. Chem. Phys. 2003, 5 , 2605-2611

FMe

Me

ClMe

Me

BrMe

Me

IMe

Me

Cl

Me

F

Me

Br

Me

I

Me

FMe

MeMe

ClMe

MeMe

BrMe

MeMe

IMe

MeMe

F

MeMe

Cl

MeMe

Br

MeMe

I

MeMe


C-F 120.6 G3

122.2 G3

121.7 G3

121.5 CBS-4M

C-Cl 83.0 G3


84.5 G3

87.8 CBS-4M


C-F

121.7

121.6

121.6

121.5

121.4

121.4

121.4

121.3

121.2


O

FHO

FMe

O

FO

F

O

ClH

O

ClMe

O

Cl

O

Cl

H2NO

F

HOO

F

H3CO

F

HO

F

FO

F

HOOCO

F

F3CO

F

NCO

F

O2NO

F


C-Cl88.3 ALL ab-initio

88.0

88.0

87.8

87.7

87.6

87.6

87.5

87.4


C-Cl 340.3 ab-initio354.1 Experimental




H2NO

Cl

HOO

Cl

H3CO

Cl

HO

Cl

FO

Cl

HOOCO

Cl

F3CO

Cl

NCO

Cl

O2NO

Cl

Cl

Cl

MeCl

MeH

ClCl


R = Li R-Cp 82.3 CCSD(T)/B//BP86/A79.0 BP86/A

R = Na 58.6 CCSD(T)/B//BP86/A54.4 BP86/A

R = K 57.9 CCSD(T)/B//BP86/A50.4 BP86/A

R = Rb 55.3 CCSD(T)/B//BP86/A50.4 BP86/A

R = Cs 60.0 CCSD(T)/B//BP86/A56.1 BP86/A

R = B 87.3 CCSD(T)/B//BP86/A94.5 BP86/A

R = Al 87.4 CCSD(T)/B//BP86/A88.4 BP86/A

R = Ga 78.3 CCSD(T)/B//BP86/A79.2 BP86/A

R = In 78.0 CCSD(T)/B//BP86/A76.7 BP86/A

R = Tl 66.0 CCSD(T)/B//BP86/A67.0 BP86/A

R = Be (D5d) R-(Cp)2 153.9 CCSD(T)/B//BP86/A146.6 BP86/A

R = Be (Cs) 154.0 CCSD(T)/B//BP86/A146.3 BP86/A

R = Mg (D5d) 121.1 CCSD(T)/B//BP86/A112.5 BP86/A

R = Mg (D5h) 121.0 CCSD(T)/B//BP86/A112.5 BP86/A

R = Ca (D5d) 154.9 CCSD(T)/B//BP86/A155.2 BP86/A

R = Sr (C1) R-(Cp)2 149.3 CCSD(T)/B//BP86/A145.3 BP86/A

R = Ba (Cs) 161.1 CCSD(T)/B//BP86/A154.3 BP86/A

R = Zn (Cs) 69.6 CCSD(T)/B//BP86/A60.9 BP86/A

R = Si (C2) 124.3 CCSD(T)/B//BP86/A131.0 BP86/A

R = Ge (Cs) 117.4 CCSD(T)/B//BP86/A123.4 BP86/A

R = Sn (Cs) 111.3 CCSD(T)/B//BP86/A116.0 BP86/A

R = Pb (C1) 106.2 CCSD(T)/B//BP86/A107.9 BP86/A

Chem. Eur. J. 2002, 8(20), 4693-4707.

R

R

R


Fe(bz)+ M = Fe Arene-M+ 207.5 Threshold-CID239.2 m -PW1PW91235.8 B3LYP

Fe(py )+ M = Fe 223.7 Threshold-CID209.2 Kinetics Method206.7 Kinetics Method

Fe(σ−py )+ M = Fe 228.6 m -PW1PW91255.1 B3LYP

Fe(π−py )+ M = Fe 186.0 m -PW1PW92185.7 B3LYP

Helvet. Chim. Acta 2003, 86 , 1008-1025

Benzene-M M = Cr+ Arene-M 40.6M = Fe+ 49.6M = Co+ 61.1

Toluene-M M = Cr+ 42.6M = Fe+ 51.8M = Co+ 63.4

Ethylbenzene-M M = Cr+ 43.5M = Fe+ 52.9M = Co+ 64.2

o -xylene-M M = Cr+ 44.3M = Fe+ 53.6M = Co+ 65.2

m -xylene-M M = Cr+ 44.3M = Fe+ 53.9M = Co+ 65.3

Eur. J. Org. Chem. 1998, 565-571

M

M

Et

M

M

M

N

M

NM

M


p- xylene-M M = Cr+ Arene-M 44.3M = Fe+ 53.8M = Co+ 65.3

Mesitylene-M M = Cr+ 45.9M = Fe+ 55.2M = Co+ 66.8

1,2,4-trimethyl- M = Cr+ 45.7benzene-M M = Fe+ 55.3

M = Co+ 66.9

Durene-M M = Cr+ 47.1M = Fe+ 56.6M = Co+ 68.2

Penta- M = Cr+ 48.2methylbenzene-M M = Fe+ 57.8

M = Co+ 69.7

Hexa- M = Cr+ 49.0methylbenzene-M M = Fe+ 58.9

M = Co+ 70.9

Phenol-M M = Cr+ 41.0M = Fe+ 50.0M = Co+ 61.0

Fluorobenzene-M M = Cr+ 36.2M = Fe+ 45.1M = Co+ 56.2

Chlorobenzene-M M = Cr+ 37.1M = Co+ 57.4

Eur. J. Org. Chem. 1998, 565-571

M

M

M

M

M

M

M

OH

M

F

M

Cl


Bromobenzene-M M = Co+ Arene-M 58.4

Iodobenzene-M M = Co+ 60.1

o -fluorotoluene-M M = Cr+ 38.8M = Fe+ 47.8M = Co+ 58.8

m -fluorotoluene-M M = Cr+ 38.5M = Fe+ 47.4M = Co+ 58.6

p -fluorotoluene-M M = Cr+ 38.5M = Fe+ 47.7M = Co+ 58.6

o -chlorotoluene-M M = Co+ 59.7

m -chlorotoluene-M M = Co+ 59.6

p -chlorotoluene-M M = Co+ 59.6

Aniline-M M = Cr+ 44.8M = Fe+ 54.0M = Co+ 64.8

Benzonitrile-M M = Cr+ 47.0M = Fe+ 47.8M = Co+ 57.8

Eur. J. Org. Chem. 1998, 565-571

M

Br

M

I

M

F

M

F

M

F

M

Cl

M

Cl

M

Cl

M

NH2

CN

M


R = CO M-R 2.5 MP2/II+//MP2/IIR = C(NH2)2 39.8R = CO 1.8R = C(NH2)2 56.7R = CO 13.7R = C(NH2)2 55.5R = CO 12.8R = C(NH2)2 59.1R = CO 11.3R = C(NH2)2 56.8R = CO 8.6R = C(NH2)2 55.1R = CO 13.0R = C(NH2)2 57.5R = CO 10.9R = C(NH2)2 55.4R = CO 35.7R = C(NH2)2 21.2R = CO 2.9R = C(NH2)2 39.0

Eur. J. Inorg. Chem. 1999, 2037-2045

(kJ/mol)Cr(CO)5L L = OH2 Cr-COax 242

L = OC Cr-COax 230L = CO Cr-L 183

Cr-COax 183L = NH3 233L = PH3 213L = PMe3 214L = N2 205

(staggered C2v) L = CF2 Cr-L 211Cr-COax 177

(staggered C2v) L = CCl2 Cr-L 223Cr-COax 166

L = CS Cr-L 249Cr-COax 167

(staggered C2v) L = CH2 Cr-L 344Cr-COax 164

(eclipsed C2v) L = CH2 Cr-L 341Cr-COax 166

L = NO+ Cr-COax 150

Mo(CO)5L L = OH2 Mo-COax 253L = OC 242L = NH3 231L = PH3 199L = PMe3 194L = N2 202L = CO Mo-L 163

Mo-COax 163van Wuellen, C. J. Comp. Chem. 1997, 18(16), 1985-1992

Cl4Ti R

F4Ti R

Cl3In R

F3In R

Cl3Ga R

F3Ga R

Cl3Al R

F3Al R

Cl3B R

F3B R

MOCOC CO

CO

L

CO


Mo(CO)5L L = CF2 (staggered C2v) Mo-L 191Mo-COax 153

L = CCl2 (staggered C2v) Mo-L 205Mo-COax 142

L = CS Mo-L 228Mo-COax 142

L = CH2 (staggered C2v) Mo-L 321Mo-COax 128

L = NO+ Mo-COax 140W(CO)5L L = OH2 W-COax 293

L = OC W-COax 278L = NH3 W-COax 269L = PH3 W-COax 233L = PMe3 W-COax 227L = N2 W-COax 233L = CO W-L 193

W-COax 193L = CF2 (staggered C2v) W-L 224

W-COax 184L = CCl2 (staggered C2v) W-L 239

W-COax 173L = CS W-L 264

W-COax 173L = CH2 (staggered C2v) W-L 362

W-COax 159L = NO+ W-L 456

W-COax 165

Cr(CO)5L L = CH2 Cr-L 344351 QR-DFT353 CCSD(T)//MP2

L = CF2 211180 MP2223

L = CCl2 223

Mo(CO)5L L = CH2 Mo-L 321335 QR-DFT353 CCSD(T)//MP2

L = CF2 191162 MP2

L = CCl2 228

W(CO)5L L = CH2 W-L 362380 QR-DFT380 CCSD(T)//MP2

L = CF2 224199 MP2

L = CCl2 239van Wuellen, C. J. Comp. Chem. 1997, 18(16), 1985-1992

MOCOC CO

CO

L

CO


∆H o

ZnMe2 Zn-C 374ZnEt2 312ZnPr2 337ZnBu2 334

Smith, D. W. J. Organomet. Chem. 1999, 585, 150-153

U(η5-C5Me5)2R2 R = Me U-Rn 300R = CH2Ph 244R = CH2SiMe3 307

U(η5-C5Me5)2R(Cl) R = Me 312R = CH2Ph 263R = Ph 358

U(η5-C5Me5)2(OSit BuMe2)(R) R = Me 317R = H 342

U{η5-C5H4(SiMe3)}3R R = Me 185R = Bu 152R = CH2SiMe3 168R = CH2Ph 149R = CHCH2 223R = 363R = I 262, 265.6R = SEt 266R = St Bu 158R = H 253.7

U(η5-C5H4t Bu)3R R = H 251.6

R = I 246.3R = SEt 252

U(C9H7)3R R = Me 195R = OCH2CF3 301R = I 267

Leal, J. P.; Marques, N.; Takats, J. J. Organomet. Chem. 2001, 632 , 209–214(kcal/mol)

Ta(CH2SiMe3)5 Ta-C 44(alkilydene formation) D1 Ta-C 67

Ta=C 126Luo, L.; Li, L.; Marks, T.J. J. Am. Chem. Soc. 1997, 119, 8574-8575

TaMe5 Ta-C 261 237Simões, J.A.M.; Beauchamp, J.L. Chem. Rev. 1990, 90 , 629-688

C C Ph


U(C9H6Et)3R R = Me U-Rn 187U(C9H6SiMe3)3R R = SEt 158

U(η5-C5H5)3R R = SiPh3 156R = GePh3 163R = SnPh3 156R = Fe(CO)2(cp) 129R = Ru(CO)2(cp) 169R = Cp 299

UR2 R = C8H8 344442190

R = C8H7Bu 417UR4 R = MeCO2 517

R = Cl 422.6UCl2R(TpMe2)3 R = CH(SiMe3)2 295

R = Cp 362R = Ot Bu 460.5R = OCMe2CH2COMe 484.2R = N(SiMe3)2 334R = (3,5-Me2pz 293

UCl2R(TpMe2)3.thf R = Thf 21.5Leal, J. P.; Marques, N.; Takats, J. J. Organomet. Chem. 2001, 632 , 209–214


RMe3 R = Si C-Me 70.62 HF and NR70.46 HF and RESC89.30 B3LYP and NR89.12 B3LYP and RESC86.37 BOP and NR86.19 BOP and RESC

R = Ge 62.99 HF and NR62.20 HF and RESC80.73 B3LYP and NR77.78 B3LYP and RESC77.67 BOP and NR76.55 BOP and RESC

R = Sn 53.22 HF and NR51.30 HF and RESC71.41 B3LYP and NR68.84 B3LYP and RESC68.91 BOP and NR66.15 BOP and RESC

R = Pb 46.09 HF and NR39.87 HF and RESC64.57 B3LYP and NR56.32 B3LYP and RESC62.28 BOP and NR53.49 BOP and RESC

Lie, W.; Fedorov, D. G.; Hirao, K. J. Phys. Chem. A 2002, 106, 7057-7061

M = Ru 110.2 GGA-BP86 XCM = Rh 114.6 GGA-BP86 XCM = Pd 113.9 GGA-BP86 XC

M = Ru 67.1 GGA-BP86 XCM = Rh 67.4 GGA-BP86 XCM = Pd 58.2 GGA-BP86 XC

Xavier, E. S.; Duarte, H. A. J. Quant. Chem. 2003, 95(2) , 164-176

M

SnCH2

M

PdCF2


MC Bond Distance (Ǻ) M-C BDE1.799 90.31.624 141.41.625 131.21.565 155.61.628 138.01.679 148.61.829 126.7

MC (Ǻ) CO (Ǻ) M-C BDE C-O BDE1.903 1.160 15.4 228.21.661 1.167 61.4 223.11.861 1.164 27.5 199.51.698 1.173 47.1 194.61.864 1.166 39.6 204.72.013 1.171 27.7 182.22.034 1.171 44.4 220.7

MC (Ǻ) M-C BDE1.750 93.70.05 157.41.625 145.8

- 183.81.65 149.3

- 189.40.50 186.00.40 189.91.82 129.91.79 139.5

MC (Ǻ) CO (Ǻ) M-C BDE C-O BDE1.975 1.160 6.03 215.31.70 1.15 3.03 148.61.70 1.17 22.55 179.7.0.02 1.23 26.16 145.31.75 1.17 28.02 181.60.05 1.22 13.65 127.21.05 1.22 17.86 134.80.90 1.25 46.24 159.32.00 1.16 33.16 206.32.05 1.19 40.95 204.4

Sosa, R. M.; Gardiol, P.; Beltrame, G. J. Quant. Chem. 1997, 65(5) , 919-928

Ni C(1)

Cu C(2)

Ni C(3)

Fe C(3)

Fe C(5)

Ti C(3)

Ti C(5)

Cu CO(2)

Ni CO(1)

Ni CO(3)

Fe CO(3)

Fe CO(5)

Ti CO(3)

Ti CO(5)

Cu5C(2)(5,0)Cu5C(2)(4,1)

Ni5C(1)(5,0)

Ni5C(1)(4,1)

Ni5C(3)(5,0)

Ni5C(3)(4,1)

Fe5C(3)(4,1)

Fe5C(5)(4,1)

Ti7C(3)(7,0)

Ti7C(5)(7,0)

Cu5CO(2)(5,0)

Cu5CO(2)(4,1)

Ni5CO(1)(5,0)

Ni5CO(1)(4,1)

Ni5CO(3)(5,0)

Ni5CO(3)(4,1)

Fe5CO(3)(4,1)

Fe5CO(5)(4,1)

Ti7CO(3)(7,0)

Ti7CO(5)(7,0)


Ti(Cp)2R2 R = Me Ti-Cp 298R = Ph 331

R = 342

R = 341

R = 340

R = 349

R = Fe 331

Mo(Cp)2R2 R = H Mo-Cp 251R = Me 166

W(Cp)2R2 R = H 305R = Me 221

Calhorda, M. J.; Dias, A. R.; da Piedade, M. E. M.; Salema, M. S.; Simoes, J. A. M. Organometallics 1987, 6, 734-738(kcal/mol) All ZPE corrected

M(CO)4 M = Ni 1.827 M-CO 26.3 BP86/II1.821 27.0 BP86/TZP

1.825, 1.817 25 ± 2 ExperimentalM = Pd 2.016 12.9 BP86/II

2.016 11.7 BP86/TZPM = Pt 1.981 14.2 BP86/II

1.976 13.5 BP86/TZPDoerr, M.; Frenking, G. Z. Anorg. Allg. Chem. 2002, 628 , 843-850

Me

Me

CF3

OMe


All singlet states, ZPE correctedFe(CO)4R R = CO Fe-R D3h 39.0 B3LYP/II//B3LYP/II

45.1 CCSD(T)/II//B3LYP/II

R = CS axial C3v 55.8 B3LYP/II//B3LYP/II64.2 CCSD(T)/II//B3LYP/II

equatorial C2v 55.4 B3LYP/II//B3LYP/II64.2 CCSD(T)/II//B3LYP/II

R = N2 axial C2v 16.5 B3LYP/II//B3LYP/II22.9 CCSD(T)/II//B3LYP/II


R = NO+ axial C3v 79.2 B3LYP/II//B3LYP/II

84.8 CCSD(T)/II//B3LYP/IIequatorial C2v 92.4 B3LYP/II//B3LYP/II


R = CN-axial C3v 87.0 B3LYP/II//B3LYP/II



R = NC- axial C3v 70.7 B3LYP/II//B3LYP/II



R = η 2-C2H4 axial Cs 18.3 B3LYP/II//B3LYP/II30.6 CCSD(T)/II//B3LYP/II


R = η 2-C2H2 axial Cs 16.9 B3LYP/II//B3LYP/II26.9 CCSD(T)/II//B3LYP/II

Yu, C.; Hartmann, M.; Frenking, G. Z. Anorg. Allg. Chem. 2001, 627 , 985-998


All singlet states, ZPE correctedFe(CO)4R R = η 2-C2H2 equatorial Fe-R C2v 25.4 B3LYP/II//B3LYP/II


R = CCH2 axial Cs 64.7 B3LYP/II//B3LYP/II75.7 CCSD(T)/II//B3LYP/II


R = CH2 axial Cs 69.1 B3LYP/II//B3LYP/II79.6 CCSD(T)/II//B3LYP/II


R = CF2 axial Cs 52.2 B3LYP/II//B3LYP/II59.8 CCSD(T)/II//B3LYP/II


R = NH3 axial Cs 29.9 B3LYP/II//B3LYP/II39.1 CCSD(T)/II//B3LYP/II

equatorial Cs 23.7 B3LYP/II//B3LYP/II33.1 CCSD(T)/II//B3LYP/II

R = NF3 axial Cs 15.3 B3LYP/II//B3LYP/II23.5 CCSD(T)/II//B3LYP/II


R = PH3 axial C3v 26.8 B3LYP/II//B3LYP/II38.9 CCSD(T)/II//B3LYP/II


R = PF3 axial C3v 34.1 B3LYP/II//B3LYP/II45.2 CCSD(T)/II//B3LYP/II


R = η 2-H2 axial Cs 10.3 B3LYP/II//B3LYP/II16.5 CCSD(T)/II//B3LYP/II


Yu, C.; Hartmann, M.; Frenking, G. Z. Anorg. Allg. Chem. 2001, 627 , 985-998


Re(η5-C5H5)(CO)2(H)(R) R = Phenyl Re-R 252.0 ALL usingRe-H 489.8 Hybrid DFT B3PW91

R = Re-R 276.9Re-H 500.5

R = Re-R 253.5Re-H 490.6

R = Re-R 255.3Re-H 494.3

R = Re-R 300.0Re-H 512.0

R = Re-R 278.7Re-H 501.2

R = Re-R 278.1Re-H 500.3

R = Re-R 279.9Re-H 504.6

R = Re-R 255.4Re-H 492.0

R = Re-R 256.1Re-H 494.5

R = Re-R 301.2Re-H 511.8

R = Re-R 302.7Re-H 515.5

R = Re-R 280.4Re-H 501.7


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

FF

F

LnRe

F

F

F

LnRe

F F

F


Re(η5-C5H5)(CO)2(H)(R) R = Re-R 280.8 ALL usingRe-H 503.6 Hybrid DFT B3PW91

R = Re-R 281.0Re-H 504.8

R = Re-R 257.4Re-H 495.0

R = Re-R 304.7Re-H 512.4

R = Re-R 304.0Re-H 514.7

R = Re-R 283.0Re-H 504.4

R = Re-R 306.7Re-H 514.7


Cr(CO)6 First Dissociation Enthalpy M-CO 154Mean Dissociation Enthalpy M(CO)6 107

Mo(CO)6 M-CO 170 M(CO)6 152

W(CO)6 M-CO 192 M(CO)6 178

Fe(CO)5 M-CO 174 M(CO)5 118


LnRe

F F

F

LnRe

F

F

F

LnRe F

F

F

LnRe

F

FF

F

LnRe

FF

F

F

LnRe

FF

F

F

LnRe

FF

F

FF

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

Th(Cp*)3R R = Me Th-C 375 351R = 350 351

R = 333 326

R = 369 365

R = 315 358

Th(Cp*)2R2 R = Me 339 315R = Et 318 308R = Bu 307 300

R = 302 295

R = 335 331

R = Ph 372 328

Th(Cp*)2(Ot Bu)R R = Me 349 326

R = Et 330 320R = Bu 316 309

R = 321 314

R = 345 341

R = Ph 387 343

Th(Cp*)2[OCH(t- Bu)2]Bu 347 340Simões, J.A.M.; Beauchamp, J.L. Chem. Rev. 1990, 90 , 629-688

LnTh

LnTh

LnThSi Me

Me Me

LnTh

LnTh

LnThSi Me

Me Me

LnTh

LnThSi Me

Me Me


Th(Cp*)2(Cl)R R = Et Th-C 313 303R = Ph 374 330R = Bz 285 328

Th(Cp*)2[(CH2)2CMe2] 274 Th(Cp*)2[(CH2)2SiMe2] 318

Th(Cp*)2(C4H6) 209 Th(Cp*)2[CH2(CMe)2CH2] 188 Th(Cp*)2(CHCH2CH2)2 368

Th(Cp*)2(OR)[C(O)H] R = 345 396

R = 351 402

U(Cp*)2[OSi(t -Bu)Me2]R R = H U-C 342R = Me 317 293

U(Cp*)2R2 R = Me 300 276R = Bz 244 287

R = 307 303

U(Cp*)2(Cl)R R = Me 312 288R = Ph 358 314R = Bz 263 306

U(Me3SiC5H4)3R R = Me 185 161R = Bu 152 145

R = 168 164

R = Bz 149 192R = CHCH2 223 185R = CCPh 363


ThLn

ThLn

LnUSi Me

Me Me

LnUSi Me

Me Me


TiR4 R = Ti-C 198 191

R = 253 249

R = Bz 201 244

Ti(Cp)2R2 R = Me 298 274R = Ph 332 288

R = 343 299

R = 342 298

R = 341 297

R = 350 306

R = (η 5-C5H4)Fe(η 5-C5H5) - 278

Ti(Cp)2Bz2 237 280

Ti(Cp)2(Cl)R R = Me - 293R = Ph - 291

Ti(Cp)2(Cl)Et 150

Ti(Cp*)2R2 R = Me 281 257R = Ph 280 236

ZrR4 R = Zr-C 249 242

R = 310 306

R = Bz 263 306

Zr(Cp)2Me2 285 261Zr(Cp)2Ph2 300 256

Zr(Cp*)2R2 R = Me 284 260R = Ph 312 268

Zr(Cp*)2CH2(CHEt)2CH2 261 - Zr(Cp*)2CH2CH2C6H4-o 282 -

Zr(Cp*)2Me3 276 252 Zr(Cp*)(OC6F5)Me2 289 265 Zr(Cp*)(OC6F5)2Me 310 286Simões, J.A.M.; Beauchamp, J.L. Chem. Rev. 1990, 90 , 629-688

LnTiSi Me

Me MeLnTi

MeMe Me

LnTi

Me

LnTi Me

LnTi CF3

LnTi OMe

LnZrMe

Me Me

LnZrSi Me

Me Me


Hf(Cp*)(CH2CMe3)4 Hf-R 266 259

Hf(Cp*)2R2 R = H 346 346R = Me 306 282R = Bu 274 267

Hf(Cp*)2H2 326 326Hf(Cp*)(H)Ph 350 306Hf(Cp*)Me3 294 270

Hf(Cp*)(OC6F5)Me2 300 276 Hf(Cp*)(OC6F5)2Me 309 285 Hf(Cp*)(C5Me4CH2CH2CH2)H 243 - Hf(Cp*)(C5Me4CH2C6H4-o )H 320 - Hf(Cp*)2(Me)C(O)Me 298 366Simões, J.A.M.; Beauchamp, J.L. Chem. Rev. 1990, 90 , 629-688

Mo(Cp)2R2 R = H Mo-R 257 -R = Me 166 142R = Et 156 146R = Bu 154 147

Mo(Cp)2(C2H4) 59 -Mo(Cp)2(C2Ph2) 120 -Mo(Cp)(CO)3H 273 -

Mo(Cp)(CO)3R R = H 282 282R = Me 203 179R = Et 185 175R = C3H5 147 195R = Bz 154 197


W-Cl 347.3WMe6 W-R 160 136

W(Cp)2R2 R = H 311 311R = Me 221 197

W(Cp)2(I)H 273W(Cp)2(CO)3H 339 339

W(CO3)[P(c-C6H11)3]2(H2) 40 W(CO)5[C(OMe)Ph] 359Simões, J.A.M.; Beauchamp, J.L. Chem. Rev. 1990, 90 , 629-688


Mn-Mn 159Mn(CO)5R R = H Mn-R 245 245

R = Me 187, 192 163, 168R = Ph 207 163R = Bz 129 172R = CH2F 139 130R = CHF2 144 141R = CF3 182, 203 156, 177

Mn(CO)5C(O)R R = Me 160, 182, 185 228, 250, 253R = Ph 127, 131 193, 197R = CF3 176 222R = Et 181 242R = Pr 175 236

Mn(CO)4(P(C6H4OMe-p )3(CH2C6H4OMe-p ) 105

Re-Re 187Re(CO)5Me Re-C 220 196


Fe(CO)4H2 Fe-H 272 244Fe(CO)4(C2H4) Fe-C 152 96

Fe(CO)(1,3-C4H6)2 178 Fe(CO)(1,3-c-C4H6)2 194Fe(CO)3(1,3-C4H6) 200Fe(CO)3(I)(C3H5) 170

Fe(CO)3(1,3,5,7-cyclooctatetraene) 179Fe(CO)3(C2H4)2 113

Ru-C Ru(2,3,7,8,12,13,17,18-octaethylporphyrinato anion)Et2 91Simões, J.A.M.; Beauchamp, J.L. Chem. Rev. 1990, 90 , 629-688


Co(CO)4H Co-C 227 227Co3(CO)9(CCl) 114Co3(CO)9(CBr) 135

Co(dimethylglyoxime)2(R)CH(Me)PhR = pyridine 113, 117, <90, <89R = 4-methylpyridine 115R = 4-aminopyridine 120, <97R = 4-cyanopyridine 106, <84R = imidazole 118, <96R = methylpyridine 91R = PMe2Ph 100R = PBu3 87R = PEtPh2 81R = PPh3 73R = P(CH2CH2CN)3 85

Co(dimethylglyoxime)2(R)BzR = PMe2Ph 128 171R = PBu3 121 164R = PEtPh2 113 156R = PPh3 108 151R = P(c-C6H11)3 96 139

Co(octaethylporphyrine)(R)BzR = PMe2Ph 114 157R = PBu3 123 166R = PEtPh2 110 153R = PPh3 100 143R = P(c-C6H11)3 124 167

Co(dimethylglyoxime)2(R)CH(CH2X)COOMeR = pyridine, X = H 120R = 4-methylpyridine, X = H 123R = 4-cyanopyridine, X = H 118R = pyridine, X = COOMe 139

Co(dimethylglyoxime)2(pyridine)RR = Me 138 114R = i -Pr 98 99R = Bz 136 179



Co(N,N' -bis(salicylidene)-o -phenylenediamine)(pyridine)RR = Pr Co-C 105 98R = i -Pr 83 84R = CH2CMe3 77 70R = Bz 91 134

Co[11-hydroxyl-2,10-diethyl-3,9-dimethyl-1,4,8,11-tetraazaundeca-1,3,8,10-tetraen-1-olato](I)RR = CH2CMe3 127 120R = Bz 109 152

Co(dimethylglyoximeBF2)2(H2O)Bz 99 142 Co(1,4,8,11-tetraazacyclotetradecane)2(H2O)Bz2+ 98 141

[cobinamide]R R = i -Pr 110 111R = CH2CMe3 126 119R = Bz 105 148R = Adenosine 144

B12R R = i -Pr 79 80R = i -Bu 104 95R = CH2CMe3 90, 99 83, 92R = Bz 95 138R = CH2C5H9 99

B12Ado 112, 125, 131Rh(Cp)(C2H4)2 Rh-C <130

Rh(octaethylporphyrine)RR = H 259 259R = C(O)H 249 300R = CH(Bu)OH 187

Rh(Cl)(B)[P(4-tolyl)3]2H2 242 242

Rh(NC3H3C6H3CO)(Cl)(pyridine)C(Ph)(OMe)H 128

Ir(R)(CO)(PPh3)2H2 R = Cl Ir-C 247 272R = Br 253R = I 258 270

Ir(Cl)(CO)(PPh3)2(R)HR = Cl 245 271R = Br 237 262

Ir(Cl)(CO)(PMePh2)2(Cl)H 266 291Simões, J.A.M.; Beauchamp, J.L. Chem. Rev. 1990, 90 , 629-688


Ir(Cl)(CO)(PR3)2H2 R = Et Ir-C 243 268R = c-C6H11 246 271

Ir(R)(CO)(X)2H2 R = Cl, X = P(i -Pr)3 240 265R = Cl, X = PBuPh2 242 267R = Cl, X = PPh3 251 276R = Cl, X = P(c-C6H11)3 240 265R = Cl, X = PBz4 249 274R = Cl, X = P(p -tolyl)3 246 271R = Cl, X = P(OPh)3 244 269R = Br, X = P(i -Pr)3 245 270R = Br, X = PPh3 235 260R = Br, X = P(c-C6H11)3 244 269R = Br, X = P(OPh)3 238 263R = I, X = P(i -Pr)3 227 252R = I, X = PPh3 229 254R = I, X = P(c-C6H11)3 256 281R = I, X = P(OPh)3 224 249

Ir(Cl)2(CO)(R)2C(O)MeR = PMe3 >237R = PEt3 >241

Ir(Cp*)(PMe3)H2 310 310

Ir(Cp*)(PMe3)(R)H R = Ph 337 293R = c-C6H11 209 216

Ir(Cp*)(PMe3)(H)R R = c-C5H9 215R = c-C5H11 244R = Ph 321 277R = c-C6H11 218 225R = 2,3-Me2Bu 240 237R = CH2CMe2Et <233

Ir(Cp*)(PMe3)Me2 243 219 Ir(Cp*)(PMe3)(Br)C2H3 326 288Simões, J.A.M.; Beauchamp, J.L. Chem. Rev. 1990, 90 , 629-688


Ir(R)(CO)(PPh3)2X R = F, X = C2F4 Ir-X 79R = F, X = C4F6 99R = Cl, X = C2F4 67R = Cl, X = C4F6 96R = Br, X = C2F4 41R = Br, X = C4F6 79R = I, X = C2F4 57R = I, X = C4F6 82


Ni(cod)2 Ni-C 209 -[Pd(C3H5)Cl]2 Pd-C - 262

cis -Pd(Cl)2(cod) - 344Pd(I)(bipy)Me3 136 -

Pt(Cp)Me3 Pt-C 163 195Pt(Cp)2Me2 - 195

trans -Pt(PEt3)2Ph2 - 159 cis -Pt(PEt3)2Me2 269 245

cis -Pt(PEt3)2(o -tolyl)2 298 254 cis -Pt(PEt3)2(Cl)Me 251 227 cis -Pt(PEt3)2(Cl)(o -tolyl) 300 256 trans -Pt(PPh3)2(Cl)H 307 307 cis -Pt(PPh3)2(I)Me 242 218 trans -Pt(PEt3)2(Cl)Et 206 196 Pt(PPh3)2(Cl)C(O)Ph >232 >288 Pt(PMe2Ph)2(Cl)(Me)2C(O)Me 306 Pt(R)2CH2CH2CH2 R = Cl 120

R = Br 122 Pt(Cl)2(R)CH2CH2CH2

R = (py)2 117R = (4-Mepy)2 113R = bipy 121

Pt(Br)2(R)CH2CH2CH2

R = (py)2 1117R = (4-Mepy)2 114R = bipy 124

Pt(PPh3)2(dpcb) 150 217, 217Simões, J.A.M.; Beauchamp, J.L. Chem. Rev. 1990, 90 , 629-688


Pt(PPh3)2R R = C2H4 Pt-C 152R = PhCHCH2 169R = cis -C2H2Ph2 194R = trans -C2H2Ph3 210R = C2Ph2 181R = C2(CN)4 277R = pcbd 177

Pt(Cl)2(cod) 398 Pt(AsMe3)(X)(Me)RX = Cl, R = C2F4 52

X = Br, R = C2F4 48X = Cl, R = C4F6 69X = Br, R = C4F6 61

Pt(AsMe2Ph)(X)(Me)RX = Cl, R = C4F6 73X = Br, R = C4F6 80



Sc-Me M+-L 247Ti-Me 226V-Me 207Cr-Me 126Mn-Me 213Fe-Me 242Co-Me 205Ni-Me 188Cu-Me 124Zn-Me 296

Y-Me 249Ru-Me 226Rh-Me 198Pd-Me 247Cd-Me 228

La-Me 231Hg-Me 285Lu-Me 190


Sc-CH2 M+-L 412Ti-CH2 391V-CH2 335Cr-CH2 226Mn-CH2 297Fe-CH2 347Co-CH2 326Ni-CH2 314Cu-CH2 268

Y-CH2 398Nb-CH2 456Rh-CH2 381

La-CH2 411Lu-CH2 ≥240



Ti-CH M+-L 508V-CH 481Cr-CH 314Fe-CH 426Co-CH 426

Nb-CH 610Rh-CH 431

La-CH 524Simões, J.A.M.; Beauchamp, J.L. Chem. Rev. 1990, 90 , 629-688

V-C M+-C 383Fe-C 397Co-C 384

Nb-C 600Rh-C 686

La-C 427Simões, J.A.M.; Beauchamp, J.L. Chem. Rev. 1990, 90 , 629-688

Sc-Me M-Me 134Ti-Me 192V-Me 155Cr-Me 172Mn-Me 126Fe-Me 155Co-Me 191Ni-Me 231Cu-Me 243Zn-Me 80



ScMe2 M+-Me 238 247TiMe2 268 226VMe2 203 207FeMe2 >160 242RuMe2 >176 226CoMe2 255 205RhMe2 >205 198NiMe2 >214 188PdMe2 >155 247ZnMe2 115 296CdMe2 109 228HgMe2 96 285

Sc(H)Me M+-Me 263 M+-H 239V(H)Me 188 202

Co(H)Me 182 195Simões, J.A.M.; Beauchamp, J.L. Chem. Rev. 1990, 90 , 629-688

ScL+ L = C2H2 M-L+326

L = C2H4 ≥147, 167L = C6H6 222

YL+ L = C2H4 >138L = C3H4 >297L = C3H6 >126L = C4H6 >238

LaL+ L = C2H4 >138L = C3H4 >297L = C3H6 >126L = C4H6 >238

TiC6H6+ >205



VL+ L = C2 V-L+ ≥527L = C2H 497L = C2H2 212L = C2H3 ≥367L = C2H4 209L = Et 234

VC3H5+ 427

VC6H6+ 260

V(C6H6)2+ 239

NbCH22+ Nb-L+

819NbC6H6

+ 276TaC6H6

+ Ta-L+ 251<D< 301CrC6H6

+ Cr-L+222

MoL+ L = C2H2 Mo-L+≥312

L = C2H4 ≥137L = 1,3-C4H6 ≥245L = C6H6 ≥250

FeC2H4+ Fe-L+

142, 174Fe(C3H5)2

+ 232FeC3H6

+ 155FeC4H6

+ 201FeCp+ >364

Fe(c- C5H6)+ 213

FeC6H4+ 318

FeC6H6+ 230

RuC2H4+ Ru-L+

>159CoC2H4

+ Co-L+155, 192

CoC3H6+ 201

CoC4H6+ <218

Co(Cp)C4H6+ >238

CoCp+ 356Co(Cp)2

+ 513Co(C6H6)

+ 285Co(PhMe)+ >201

CoSiH2+ 271

RhC2H4+ Rh-L+

>159RhC4H6

+ >236RhC6H6

+ 276Simões, J.A.M.; Beauchamp, J.L. Chem. Rev. 1990, 90 , 629-688

Compound Bond Dissociation Enthalpy (kJ/mol)Bond (C-Y) Energy Proton Affinity

NiC2H4+ Ni-L+

155Ni(C2H4)2

+ 180NiC3H5

+ 243NiC6H6

+ 285NiCF2

+ 196NiSiH2

+ 271CuC6H6

+ Cu-L+209


Ni(Cp)+-L L = PH3 Ni(Cp+)-L 190.4 -58.2L = MeOH 190.8 -84.1L = NO 192.0 -78L = Me2O 196.2 -49.8L = MeCHO 196.7 -67.4L = MeSH 197.1 -68.6L = EtOH 198.7 -61.5L = HCN 199.2 -109.2L = EtCHO 201.3 -56.9L = i -PrCHO 205.4 -49.0L = C2H3CHO 206.3 -59.8L = i -PrOH 207.1 -43.9L = t -BuCHO 207.5 -52.3L = Me2CO 212.1 -32.6L = i -BuOH 212.5 -41.8L = MeOAc 213.0 -41.4L = Et2O 213.0 -19.2L = Me2S 213.8 -18.0L = NH3 218.8 0L = MeCN 222.6 -59.0L = MeNH2 231.0 38.1L = NMe3 236.0 80.8L = Me2NH 237.7 64.9L = AsMe3 239.3 36.4L = MeNC 241.0 -26.4L = PMe3 241.0 86.6


Mn(CO)5L L = H Homolytic Mn+-L 172L = Me 137, 132L = CH2F 82L = CHF2 58L = CF3 72, 93L = Bz 153L = Mn(CO)5 166


Compound Bond Dissociation Enthalpy (kJ/mol)Bond (C-Y) Energy Hydride/Electron Affinity

Cr(CO)6 D [M(CO)-n -1-CHO] ≤147 184 / ≤201

Mo(CO)6 ≤172 184 / ≤192W(CO)6 ≤194 184 / ≤192Fe(CO)5 187 235 / 232


M-C M = Sc M-C 444M = Ti 423M = V 423

M = Y 418M = Zr 561M = Nb 568M = Mo 482M = Tc 564M = Ru 648M = Rh 580M = Pd 436

M = La 463M = Hf 540M = Os 649M = Ir 631M = Pt 610


M-C2 M = Sc M-C2 572M = Ti 573M = V 578M = Cr 451

M = Y 638M = Zr 581M = Nb 656M = Mo 500M = Ru 519M = Rh 433

M = La 659M = Hf 674


pyCo(dimethylglyoxime)2CH3 Co-C 33.1 pyCo(dimethylglyoxime)2CH2C6H5 31.2 pyCo(dimethylglyoxime)2CH(CH3)2 21.3Toscano, P. J.; Seligson, A. L.; Curran, M. T.; Skrobutt, A. T.; Sonnenberger, D. C. Inorg. Chem. 1989, 28, 166-168

Compound Bond Dissociation Enthalpy (kcal/mol)Bond (C-Y) Energy Hydride/Electron Affinity

CH3Co(Salen)H2O Co-C 168 CH3Co(Salen)imidazole 152 CH3Co(Salen)benzimidazole 136 CH3Co(Salen)pyridine 127 C2H5Co(Salen)H2O 125 n -C4H9Co(Salen)H2O 107

n -C4H9Co(Salen) 108 i -C4H9Co(Salen)H2O 90 i -C3H7Co(Salen)H2O 81 i -C3H7Co(Saloph)pyridine 84 i -C3H7Co(DH)2pyridine 89Li, G.; Zhang, F. F.; Chen, H.; Yin, H. F.; Chen, H. L.; Zhang, S. Y. J. Chem. Soc. Dalton Trans. 2002, 105-110

M = Y M-C 66.9M = Zr 58.6M = Nb 56.6M = Mo 45.3M = Tc 47.7M = Ru 48.5M = Rh 52.0M = Pd 41.6M = H M-H 102.7



Siegbahn, P. E. M. J. Phys. Chem. 1995, 99 , 12723-12729

M CH3

M

M H






MMe

MMe

MMe

Me


R1 = SC7H7, R2 = NO2 C-R1 heterol. 12.95homolysis 26.95radical cation -14.3

R1 = SC7H7, R2 = Br heterolysis 17.85homolysis 25.74radical cation -18.1

R1 = SC7H7, R2 = Cl heterolysis 18.38homolysis 23.96radical cation -24.3

R1 = SC7H7, R2 = H heterolysis 20.17homolysis 24.57radical cation -21.9

R1 = SC7H7, R2 = Me heterolysis 20.75homolysis 23.68radical cation -24.8

R1 = SC7H7, R2 = OMe heterolysis 21.61homolysis 23.50radical cation -24.8

R1 = S-TPCP, R2 = NO2 heterolysis 14.44homolysis 44.16radical cation -14.3

R1 = S-TPCP, R2 = Br heterolysis 17.80homolysis 41.41radical cation -17.3

R1 = S-TPCP, R2 = Cl heterolysis 18.09homolysis 39.40radical cation -19.5

R1 = S-TPCP, R2 = H heterolysis 20.14homolysis 40.27radical cation -18.6

R1 = S-TPCP, R2 = Me heterolysis 20.75homolysis 39.38radical cation -19.6

R1 = S-TPCP, R2 = OMe heterolysis 21.90homolysis 39.52radical cation -19.6

Venimadhavan, S.; Amarnath, K.; Harvey, N.G.; Cheng, J.-P; Arnett, E.M. .J. Am. Chem. Soc., 1992, 114(1) , 221-229

R1 R2


R1 = S-9-PhXan, R2 = NO2 C-R1 heterol. 18.33homolysis 26.1radical cation -10.4

R1 = S-9-PhXan, R2 = Br heterolysis 23.05homolysis 24.71radical cation -13.1

R1 = S-9-PhXan, R2 = Cl heterolysis 24.36homolysis 23.71radical cation -14.6

R1 = S-9-PhXan, R2 = H heterolysis 26.11homolysis 24.29radical cation -13.6

R1 = S-9-PhXan, R2 = Me heterolysis 26.94homolysis 23.64radical cation -14.8

R1 = S-9-PhXan, R2 = OMe heterolysis 27.85homolysis 23.51radical cation -15.0

R1 = S-Xan, R2 = NO2 heterolysis 21.66homolysis 29.32radical cation -6.27

R1 = S-Xan, R2 = Br heterolysis 24.70homolysis 26.25radical cation -9.45

R1 = S-Xan, R2 = Cl heterolysis 25.87homolysis 25.11radical cation -10.4

R1 = S-Xan, R2 = H heterolysis 26.43homolysis 24.49radical cation -11.1

R1 = S-Xan, R2 = Me heterolysis 27.16homolysis 23.75radical cation -11.8

R1 = S-Xan, R2 = OMe heterolysis 27.67homolysis 23.22radical cation -12.3

R1 = SCPh3, R2 = NO2 radical cation -11.0R1 = SCPh3, R2 = Br radical cation -14.7R1 = SCPh3, R2 = Cl radical cation -15.0R1 = SCPh3, R2 = H radical cation -14.5R1 = SCPh3, R2 = H radical cation -15.3R1 = SCPh3, R2 = Me radical cation -15.3R1 = SCPh3, R2 = OMe radical cation -16.0

Venimadhavan, S.; Amarnath, K.; Harvey, N.G.; Cheng, J.-P; Arnett, E.M. .J. Am. Chem. Soc., 1992, 114(1) , 221-229

R1 R2


C-OO. trans, cis dissociated radical 19.6, 23.1 B3P86-HLM

as trans or cis

20.5, 21.3 B3P86-HLM

7.9, 7.4 B3P86-HLM

8.4, B3P86-HLM

14.2, 77.4 B3P86-HLM

14.6, 77.7 B3P86-HLM

4.2 B3P86-HLM

6.0 B3P86-HLM

9.8, 11.2 B3P86-HLM

11.7, 12.9 B3P86-HLM

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

C-O 92.183.2

C-N 85.261.0


R = OOR = OO

HO CH3

MeO CH3

H2N CH3

O2N CH3

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-O 92.194.0

95.5

95.8

80.1

112.4

82.6

109.5

109.9


C-OMe 83.2

85

85.8

84

101

38

99.6

100


C-NH2 85.284.8

86.0

85.7

104.2

71.7


HO CH3

MeHO

Me

MeHO

Me Me

HO

OH

O

OHHO

OHMe

MeO CH3

MeMeO

Me

MeMeO

Me Me

OMe

MeO OMeO

OMeH

O

OMeMe

H2N CH3

H2NCH3

MeH2N

Me

MeH2N

Me Me

NH2

O

NH2Me

MeOCH3

HOCH3

OH

NH2


C-NO2 61.0

61.6

62.9

62.8

72.5

50.5


C-O106.3

92.1

90.5

174

154

178.8

28

109.3

100

74

38


O2N CH3

O2NCH3

MeO2N

Me

MeO2N

Me Me

NO2

NO2

H2C OH

C OH

H

C OH

OH

H

OOH

OOH

H

HO

O

OMe

Me

O HMe

OMe

Me

OMe

H3C OH

H3C O


C-O 59.3 DFT I65.2 DFT II63.5 DFT III65.3 Experimental

52.8; 52.5 DFT II

-9.2 DFT I-9.5 DFT II-8.9 DFT III

-9.3 DFT II

-1.4 DFT II

-6.0 DFT I-6.1 DFT II-5.5 DFT III

-6.1 DFT II

-0.5 DFT II

3.7 DFT I3.0 DFT II2.8 DFT III

3.0 DFT II

-0.1 DFT II

5.2 DFT I4.6 DFT II4.5 DFT III

4.7 DFT II

-0.9 DFT II

-4.5 DFT II-4.7 DFT III

Pratt, D. A.; de Heer, M. I.; Mulder, P.; Ingold, K. U. J. Am. Chem. Soc. 2001, 123 , 5518-5526

O

OH2N

ONH2

OMeO

OOMe

OF3C

OCF3

OO2N

ONO2

OCH3

OCH3

H2N

OCH3

MeO

OCH3

F3C

OCH3

O2N

OCH3

HO

O


C-O 62.6 Experimental

62.3 Experimental

61.2 Experimental

62.2 Experimental

67.5 Experimental

58.1 Experimental

Pratt, D. A.; de Heer, M. I.; Mulder, P.; Ingold, K. U. J. Am. Chem. Soc. 2001, 123 , 5518-5526(kJ/mol)

C-N 356C-O 385.7C-S 307.8


C-O 80.9 DFT-AM166.3 Experimental68.8 Corrected




C-S 56.3 DFT-AM149.6 Experimental47.4 Corrected



H3C N

H3C O

H3C S

H3C OMe

Me Me

H3C O

H3C O

H3C OSMe

S

O

Me

O

S

O

Me

O

OCH3

HO

OCH3

HO

O

OCH3

OH

OCH3

OMe

OCH3

MeO

OCH3

F3C


C-N 89.4 DFT-AM184.9 Experimental84.9 Corrected











C-O 78.8 Experimental74.3 B3LYP/6-31G(d), 298K



H3C NH2

NH2

NHMe

N CH3MeN

NEtNMe

NNMe

Me

MeMe

NNMe

Me

MeMeMe

Me

NO2Me

NO

NO

FF

F

F F

O

O


C-H 97 Photoacoustic CalorimetryC-OO 24 (PAC)

C-H 77 Photoacoustic CalorimetryC-OO 12, 13 (PAC)

C-H 88.2, (87) DFT, (Expt)C-OO 27.8, (10) DFT, (Expt)

C-H 89.9, 89 DFT, (Expt)C-OO 30.2 (25,24) DFT, (Expt)

C-H 90.7, 91.6, (92) DFT, (Expt)C-OO 32.4, (32) DFT, (Expt)

C-H 94.6, (96) DFT, (Expt)C-OO 31.6, (34) DFT, (Expt)

C-H 105.0, 105.7 DFT105 Experimental

C-OO 31.4, 31.1 DFT33 Experimental


C-OO 32.4 DFT35 Experimental


C-OO 33.0 DFT





C-H 106.4, 107.2 DFT

C-OO 39.5 DFTKranenburg, 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

H3C OO

C2H5 OO

C2H5 H

C3H7 H

C3H7 OO

MeMe

H

MeMe

OO

MeMe

H

MeMe

OO

c-C3H5 H

c-C3H5 OO


C-H 97.3, 98.0 DFT

C-OO 34.2 DFT



C-H 109.3 DFT111 Experimental

C-OO 45.2 DFT

C-H 105.7 DFT

C-OO 44.1 DFT


C-OO 46.2 DFT




C-OO 14.9 DFT






c-C4H7 H

c-C4H7 OO

c-C6H11 OO

c-C6H11 H

C2H3 H

C2H3 OO

Me

HMe

OO

H

OO

H

OO

HMe

OOMe

c-C6H7 OO

c-C6H7 H

H

OO



C-OO 18.9 DFT




C-OH108.7 G3

109.2 G3

108.9 G3

109.9 CBS-4M


C-OH109.2

109.7

109.8

109.9

110.1

110.4

110.6

110.7

110.9


OO

Me

H

Me

Cl3C H

Cl3C OO

O

OHH

O

OHMeO

OHO

OH

H2NO

OH

HOO

OH

H3CO

OH

HO

OH

FO

OH

HOOCO

OH

F3CO

OH

NCO

OH

O2NO

OH


C-O 110.2 G2110.5 G2MP2110.3 G2MS

108.8 G2109.3 G2MP2109.1 G2MS

109.9 G2MP2109.8 G2MS

108.1 G2MP2108.1 G2MS

C-N 80.8 G281.4 G2MP283.2 G2MS75.3 Experimental

99.8 Experimental

C-S 73.2 G274.1 G2MP274.7 G2MS73.6 Experimental

78.4 Experimental


C-N99.1 G3

98.5 G3

98.9 G3

99.8 CBS-4M


F3C OCF3

F3C OCF3

F F

F3C OCF3

F F

H3C NMe

Me

F3C NCF3

CF3

H3C SMe

F3C SCF3

O

NH2H

O

NH2Me

O

NH2O

NH2

F3C OMe


C-SMe77.5 ALL ab-initio

77.9

78.1

78.3

78.4

78.9

79.1

79.3

79.5

C-NH2 98.2

99.1

99.4

99.8

99.7

100.7

100.8

101.0

101.3


H2NO

SMe

HOO

SMe

H3CO

SMe

HO

SMe

FO

SMe

HOOCO

SMe

F3CO

SMe

NCO

SMe

O2NO

SMe

H2NO

NH2

HOO

NH2

H3CO

NH2

HO

NH2

FO

NH2

HOOCO

NH2

F3CO

NH2

NCO

NH2

O2NO

NH2


C-O 22.2 B3P86-MLM21.8 Experimental

20.6 B3P86-LLM21.2 B3P86-MLM19.8 B3P86-MLM19.7 G3MP219.0 G318.4 Experimental

15.3 B3P86-LLM15.0 B3P86-MLM14.0 B3P86-MLM15.1 G3MP213.9 G313.4 Experimental

Pratt, D. A.; Mills, J. H.; Porter, N. A. J. Am. Chem. Soc. 2003, 125 , 5801-5810 Reference includes radical stabilization energies

OO

OO

OO


O-O 172.5172.3

I-I 151.3Cl-Cl 243.36

Leal, J. P.; Marques, N.; Takats, J. J. Organomet. Chem. 2001, 632 , 209–214

O-H 87.2 Experimental79.3 B3LYP/6-31G(d), 298K83.1 B3LYP/6-311++G(d,p), 298K

O-H 84.3 Experimental74.8 B3LYP/6-31G(d), 298K79.8 B3LYP/6-311++G(d,p), 298K


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


(Solvent)O-H 86.2 isooctane

88.0 CCl486.3 benzene88.3 acetonitrile88.3 ethyl acetate94 DMSO96 NEt3

87.4 solution average87 gas phase84 benzene87 benzene87 various


tBuO OtBu

I I

Cl Cl

OH

O H

OH

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

M-M 40.6 GGA-BP8637.1 GGA-BPD9146.6 GGA-PD9146.1 Experimental

33.0 GGA-BP8629.7 GGA-BPD9132.4 GGA-PD91

56.8, 32.3, 18.08, 26.7 Experimental

33.9 GGA-BP8625.5 GGA-BPD9131.8 GGA-PD9125.0 Experimental






Xavier, E. S.; Duarte, H. A. J. Quant. Chem. 2003, 95(2) , 164-176

Ru Ru

Rh Rh

Pd Pd

Sn Sn

Ru Sn

Rh Sn

Pd Sn

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

M(BMe)4 M = Ni M-BMe 87.2 BP86/II87.9 BP86/TZP

M = Pd 72.5 BP86/II70.2 BP86/TZP

M = Pt 85.5 BP86/II83.4 BP86/TZP

M(AlMe)4 M = Ni M-AlMe 59.4 BP86/II62.9 BP86/TZP

M = Pd 50.4 BP86/II51.4 BP86/TZP

M = Pt 60.4 BP86/II60.6 BP86/TZP

M(GaMe)4 M = Ni M-GaMe 47.5 BP86/II51.5 BP86/TZP

ExperimentalM = Pd 38.0 BP86/II

39.9 BP86/TZPM = Pt 46.4 BP86/II

48.0 BP86/TZPExperimental

M(InMe)4 M = Ni M-InMe 48.2 BP86/II44.9 BP86/TZP

ExperimentalM = Pd 40.7 BP86/II

35.0 BP86/TZPM = Pt 48.6 BP86/II

41.5 BP86/TZP

M(TlMe)4 M = Ni M-TlMe 35.6 BP86/II34.0 BP86/TZP

M = Pd 25.2 BP86/II24.2 BP86/TZP

M = Pt 29.4 BP86/II27.8 BP86/TZP

Doerr, M.; Frenking, G. Z. Anorg. Allg. Chem. 2002, 628 , 843-850 Reference includes bond distances


Sn-H 78 isooctane

Si-H 96 isooctane

91 isooctane

84 isooctane

Ge-H 87 benzene

86 benzene

88 benzene

86 benzene

85 benzene

85 benzene

87 benzene

Si-H 90 benzene

N-H 91 benzene

S-Cl 70 benzene

71 benzene

N-H 90 benzene

87 benzene


Si H3

Si SiMe

Me Me

MeHMe

Si SiMe

MeHMe

3

Ge HMe

MeMe

Ge HEt

EtEt

Ge HBu

BuBu

Ge HH

PhH

Ge HPh

PhPh

Ge HH

PhPh

Si HMeS

MeSMeS

Si HSMe

Me

3

NH

Me

Me

S

O

O

ClMe

S

O

O

ClPh

HN

H

NH

SnMe H


O-H 87.8

88

85

84

88.144

89.4

94

112

≥ 96

112

111

104.6

S-H 87.4

C-H 94

O-H 104.7

105.7

106.3

90N-O 42


H3C OH

H3C SH

SH

H

OMe

MeMe

H

Ph OH

OMe

MeH

H

O HOH

O HOMe

O HOEt

O HO

Me

MeMe

O

HHO

HMeO

HH

O

HOH

O

MeOH

O

PhOH

O

HOH

O2N OMe

OH

Me


H-Y 104.206107.6

118.82101.76110.21

115.291.284.149.579.1

101.7

91.783


O-H30.2

104.6

5

112

85

O-O 47

65


H H

H OH

H O

H O

H O

H SH

H SH NO

H ON O

H ON O

O

H SiH3

H GeH3

OOH

OOH

H

OMe

Me

O HMe

OMe

Me

O HMe

H NH2

CH2 OH

H3C OH

OMe

Me

OMe


Th(Cp*)2(OR)H Th-O 518.8R = Th-OR 389 389

R = 384 384

[Th(Cp*)2H2]2 Th-H 390

Ti-Cl4 Ti-Cl 430.5

Zr-Cl 491.4Zr(Cp*)2R2 R = H Zr-H 339 339

Hf-Cl 497.6

Mn-Mn 159

Mn(CO)5R R = H Mn-H 245 245Re-Re 187

Fe(CO)4H2 Fe-H 272 244Simões, J.A.M.; Beauchamp, J.L. Chem. Rev. 1990, 90 , 629-688

OThLn

OThLn

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

Sc-H M-H 202Ti-H 197V-H 172

Cr-H 172Mn-H 126Fe-H 191Co-H 190Ni-H 243

Cu-H 255Zn-H 86

Mo-H 208Ru-H 234Rh-H 247Pd-H 234Ag-H 215Cd-H 69.0

Au-H 292Pt-H 352Yb-H 159


Sc-H M+-H 239Ti-H 227V-H 202


Cu-H 92Zn-H 231

Y-H 261Zr-H 230

Nb-H 226Mo-H 176Ru-H 172Rh-H 151Pd-H 197Ag-H 67

La-H 243Lu-H 204U-H 208



Sc-H M-H+ 918Ti-H 881V-H 864


Cu-H 658Zn-H 637

Y-H 973Zr-H 906

Nb-H 902Mo-H 803Ru-H 783Rh-H 736Pd-H 704Ag-H 648

La-H 1017Lu-H 992U-H 995


Cr-H M--H 162Mn-H >210Fe-H 265Co-H 191Ni-H 177


Cr-H M-H- 153Mn-H 137Fe-H 208Co-H 182Ni-H 217



Sc-H M+-H- 762Ti-H 782V-H 750


Cu-H 928Zn-H 919

Mo-H 820Ru-H 863Rh-H 902Pd-H 966Ag-H 874Cd-H 864

Au-H 1109Pt-H 1110Yb-H 689


Sc-H M--H+ 1496Ti-H 1501V-H 1433

Cr-H 1419Mn-H >1438Fe-H 1488Co-H 1438Ni-H 1443

Cu-H 1448Zn-H >1398

Mo-H 1448Ru-H 1445Rh-H 1449Pd-H 1492Ag-H 1402Cd-H >1380

Au-H 1381Pt-H 1458


Cd-H 49Au-H >113Hg-H 6



ScH2 M+-H 244 239YH2 272 261

LaH2 266 243LuH2 207 204CoH2 209 195

Sc(H)Me M+-Me 263 M+-H 239V(H)Me 188 202

Co(H)Me 182 195Simões, J.A.M.; Beauchamp, J.L. Chem. Rev. 1990, 90 , 629-688

Proton Affinity (kJ/mol)Ni(Cp)+-L L = PH3 M(Cp+)-L 190.4 -58.2

L = MeOH 190.8 -84.1L = NO 192.0 -78L = Me2O 196.2 -49.8L = MeCHO 196.7 -67.4L = MeSH 197.1 -68.6L = EtOH 198.7 -61.5L = HCN 199.2 -109.2L = EtCHO 201.3 -56.9L = i -PrCHO 205.4 -49.0L = C2H3CHO 206.3 -59.8L = i -PrOH 207.1 -43.9L = t -BuCHO 207.5 -52.3L = Me2CO 212.1 -32.6L = i -BuOH 212.5 -41.8L = MeOAc 213.0 -41.4L = Et2O 213.0 -19.2L = Me2S 213.8 -18.0L = NH3 218.8 0L = MeCN 222.6 -59.0L = MeNH2 231.0 38.1L = NMe3 236.0 80.8L = Me2NH 237.7 64.9L = AsMe3 239.3 36.4L = MeNC 241.0 -26.4L = PMe3 241.0 86.6


Compound Bond Dissociation Enthalpy (kJ/mol)Bond (C-Y) Energy Electron Affinity

Mn-Mn 159Mn-H 245

R+-H R = V(CO)6 R+-H 220R = Cr(CO)6 230R = Cr(CO)2(Cp)NO 207R = Cr(CO)3(Cp)Me 244R = Cr(CO)3Bz 221R = Mo(CO)6 260R = W(CO)6 257R = Mn(CO)5H 349R = Mn(CO)5Me 267R = Cr(CO)3(MeC5H4) 283R = Mn(CO)10 204R = Re(CO)5Me 294R = Re2(CO)10 246R = MnRe(CO)10 <267R = Fe(CO)5 299R = Fe(Cp)2 215, 198, 202R = Fe(CO)2(Cp)Me 210R = Ru(Cp)2 271R = Co(CO)2(Cp) 245R = Rh(CO)2(Cp) 287R = Ni(CO)4 248R = Ni(Cp)2 215R = Ni(Cp)NO 315

Mn(CO)5H LnM--H+ 1331 ≤245

Fe(CO)4H2 1334 232Co(CO)4H ≤1314 ≥227Fe(CO)4H ≥1335 232

Simões, J.A.M.; Beauchamp, J.L. Chem. Rev. 1990, 90 , 629-688(kcal/mol)

pyCo(dimethylglyoxime)2I Co-I 34.6Toscano, P. J.; Seligson, A. L.; Curran, M. T.; Skrobutt, A. T.; Sonnenberger, D. C. Inorg. Chem. 1989, 28, 166-168


M-O M = Sc M-O 681M = Ti 672M = V 625M = Cr 429M = Mn 403M = Fe 390M = Co 384M = Ni 381M = Cu 270M = Zn 271

M = Y 719M = Zr 776M = Nb 769M = Mo 560M = Tc 548M = Ru 528M = Rh 405M = Pd 381M = Ag 221M = Cd 236

M = La 801M = Hf 801M = Ta 799M = W 672M = Re 627M = Os 598M = Ir 414M = Pt 391M = Au 223M = Hg 213

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

H2O OH O-H 499 463.5H2CO HCO 372 423.4MeOH 438 451.2

MeC(O)H 359 426.6EtOH EtO 436 451.2

MeCHOH 389 401.7EtC(O)H 366 426.6

MeC(O)CH3 411 410.8PrOH 432 451.2

i -PrOH 438 451.2PrC(O)H 366 426.6

BuOH 430 451.2s -BuOH 443 451.2i -BuOH 440 451.2t -BuOH 440 451.2



O-O 27.2 DFT-AM137.6 Experimental

35.0 DFT-AM146.3 Experimental






N-N 66.5 DFT-AM170.8 Experimental




OO

CF3

F3CCF3

F3C CF3

F3C

OO

Me

MeMe

Me MeMe

OO

Me

MeMe

Me

OO

Me

Me

OO Me

Me

OO

H

Me

MeMe

OO

O

OMe

Me

HN NH2Me

H2N NH2

N NH2Me

Me


H-H 79.5 HF95.8 MP2106.4 B3LYP104.2 Experimental


136.25103.1587.5471.32


M = Y M-H 70.0M = Zr 58.8M = Nb 63.0M = Mo 54.0M = Tc 52.1M = Ru 62.4M = Rh 68.2M = Pd 53.4M = H H-H 104.8


4-methoxythiophenol R = OMe S-H heterol. 31.92heterolysis 27.85 9-Phenylxanthylium (rxn)

27.67 xanthylium (rxn)21.90 triphenylcyclopropenylium21.61 triopylium (rxn)23.80 perinaphthenium (rxn)29.24 4,4'-dimethoxydiphenylmethyl11.47 triphenylpyrylium (rxn)30.24 9,9-dimethyl-10-phenyl-

9,10-dihydroanthraceniumhomolysis 77.3

23.51 9-Phenylxanthylium (rxn)23.22 xanthylium (rxn)39.52 triphenylcyclopropenylium23.56 triopylium (rxn)11.65 perinaphthenium (rxn)27.16 4,4'-dimethoxydiphenylmethyl16.77 triphenylpyrylium (rxn)20.85 9,9-dimethyl-10-phenyl-

9,10-dihydroanthraceniumVenimadhavan, S.; Amarnath, K.; Harvey, N.G.; Cheng, J.-P; Arnett, E.M. .J. Am. Chem. Soc., 1992, 114(1) , 221-229

H H

M H

H FH Cl

H Br

H I

R SH


4-nitrothiophenol R = NO2 S-H heterol. 23.34heterolysis 18.33 9-Phenylxanthylium (rxn)

21.66 xanthylium (rxn)14.44 triphenylcyclopropenylium12.95 triopylium (rxn)16.19 perinaphthenium (rxn)19.09 4,4'-dimethoxydiphenylmethyl22.60 9,9-dimethyl-10-phenyl-


26.10 9-Phenylxanthylium (rxn)29.32 xanthylium (rxn)44.16 triphenylcyclopropenylium26.95 triopylium (rxn)27.42 4,4'-dimethoxydiphenylmethyl24.32 9,9-dimethyl-10-phenyl-

9,10-dihydroanthracenium4-bromothiophenol R = Br heterolysis 26.87

23.05 9-Phenylxanthylium (rxn)24.70 xanthylium (rxn)17.80 triphenylcyclopropenylium17.85 triopylium (rxn)18.50 triopylium (rxn)23.50 4,4'-dimethoxydiphenylmethyl24.75 9,9-dimethyl-10-phenyl-


24.71 9-Phenylxanthylium (rxn)26.25 xanthylium (rxn)41.41 triphenylcyclopropenylium25.74 triopylium (rxn)12.34 perinaphthenium (rxn)27.42 4,4'-dimethoxydiphenylmethyl21.36 9,9-dimethyl-10-phenyl-

9,10-dihydroanthracenium4-chlorothiophenol R = Cl heterolysis 27.53





R SH


thiophenol R = H S-H heterol. 29.25heterolysis 26.11 9-Phenylxanthylium (rxn)

26.43 xanthylium (rxn)20.14 triphenylcyclopropenylium20.37 triopylium (rxn)22.42 perinaphthenium (rxn)26.47 4,4'-dimethoxydiphenylmethyl9.05 triphenylpyrylium (rxn)27.08 9,9-dimethyl-10-phenyl-



9,10-dihydroanthracenium4-methylthiophenol R = Me heterolysis 29.90





R SH


N-H 110.6 DFT-AM1110.0 Experimental




O-H 116.8 DFT-AM1119.0 Experimental








S-H 90.9 DFT-AM190.5 Experimental



H2N H

ON H

F2N H

N3 H

HO H

MeO H

O H

O HOH

O

HOH

O

MeOH

O NOH

O NO2

H

HS H

MeS H

Documents

8_Bond Dissociation Enthalpy Data