Tabulated BDEs of C–H bonds | 6 | Handbook of Bond Dissociation Energi

ABSTRACT

Z,Z-2,8-decediene CH3CH=CH(CH2)4CH=CHCH3

(1) 78.0±1.0 (2) 84.7

(1) 76.3±1.0 (2) 84.3

80.3

79.3

83.4

81.9

83.6

81.6

83.4

326.4±4.2 354.3

319.2 352.8

336.1

332.0

348.9

342.7

349.8

341.6

348.8

(1) Iodination (2) Correlation

Correlation

(1) 1973ROD/WU (2) 2001TUM/DEN

2001TUM/DEN

2000DEN/DEN

2001TUM/DEN

bromide Ph3P

3-phenyl-allyl triphenyl phosphonium bromide Ph3P

81.0

338.9

AOP

1996ZHA/FRY

BDEs The broken bonds

(boldface = (boldface =

recommended data; dissociated atom)

references in parentheses) Methods

∆fHo(R), kcal/mol (references in (kJ/mol) kcal/mol kJ/mol parentheses) References

Table 3.3 C-H BDEs in Cyclic Hydrocarbons

cyclopropene

∆fHo(R) = 105.1±4.1 (439.7±17.2)

cyclopropane

∆fHo(R) = 66.9±0.3 (279.9±1.3)

methylcyclopropane

∆fHo(R) = 51.1±1.6 (213.8±6.7)

90.4±4.0

(1) 101±3

(2) 100.2±0.4 (3) 106.3±0.25 (4) 105.9±2.7 (5) 102.5

97.4±1.6

378.3±12.6

422.6±12.6

419.3±1.7 444.8±1.0 443.1±11.3 429.0

407.5±6.7

ICR

(1) Polanyi correlation

(2) Kinetics (3) VLPP (4) ICR (5) Correlation

Iodination

1980DEF/MCI

(1) 1966KER

(2) 1978APP/KLU (3) 1979BAG/BEN (4) 1980DEF/MCI (5) 2001TUM/DEN

1971MCM/GOL

(continued)

BDEs The broken bonds

(boldface = (boldface =

recommended data; dissociated atom)

references in parentheses) Methods

∆fHo(R), kcal/mol (references in (kJ/mol) kcal/mol kJ/mol parentheses) References

cyclobutane

∆fHo(R) = 51.4±1.0 (215.1±4.2)

6,6-dimethylfulvene

1,3-cyclopentadienes, substituted

at 1 site H ∆fHo(R) = 63.9±2.0

(267.4±8.4) at 1,4 site Ph2

(1) 95±3

(2) 96.5

(3) 96.8±1.0 (4) 97.8±0.3 (5) 100.0

84.5

86.5±2

(1) 82.9±2.2 (2) 81.2 (3) 83.9±0.5 (4) 81.5±2.7 (5) 82.5±1

(6) 75

397.5±12.6

403.8

405.0±4.2 409.2±1.3 418.5

353.5

361.9±8.4

346.9±9.2 339.7 351.0±2.1 341.0±11.3 345.2±4.2

313.8

(1) Polanyi correlation

(2) Polanyi correlation

(3) Iodination (4) Kinetics (5) Correlation

AOP

VLPP

(1) ICR (2) AOP (3) Electrochem. (4) ICR (5) Reflected

shock tube

(6) AOP

(1) 1966KER

(2) 1971FER/WHI

(3) 1972MCM/GOL (4) 1978APP/KLU (5) 2001TUM/DEN

1989BOR/HAR

1981STE

(1) 1980DEF/MCM (2) 1988BOR/CHE (3) 1991PAR/HAN (4) 1997ROM/JAN (5) 2001ROY/BRA

(6) 1991BOR/CHE

substituted

R = Me ∆fHo(pentamethyl-cyclopentadienyl) = 16.1±1.0

(67.4±4.2)

cyclopentene

∆fHo(R) = 38.4±1.0 (160.7±4.2)

cyclopentane, substituted

∆fHo(R) = 25.3±1.0 (105.9±4.2)

X = H

X = Me

X = Et

X = Ph

3-tert-butylbicyclo[1.1.1]- pentane

(1) 77

(1) 78 (2) 74.1

(1) 82.3±1 (2) 82±2 (3) 81.9

(1) 94.9±1 (2) 95.0±2 (3) 96.0±0.2 (4) 95.6±1 (5) 97.6

(5) 93.7

(6) 81.9

109.7±3.3

322.2

326.4 310.0

344.3±4.2 343.1±8.4 342.5

397.1±4.2 397.5±8.4 401.7±0.8 400.0±4.2 408.5

392.2

392.3

342.7

459.0±13.8

(1) AOP

(2) Pyrolysis

(1) Iodination (2) AE (3) Correlation

(1) Iodination (2) AE (3) Kinetics (4) Radical buffer (5) Correlation

(6) Correlation

GPA

(1) 1989BOR/HAR

(2) 1995ROT/HUN

(1) 1970FUR/GOL(b) (2) 1976LOS/TRA (3) 2000DEN/DEN

(1) 1970FUR/GOL (2) 1976LOS/TRA (3) 1978APP/KLU (4) 1982CAS/GRI (5) 2001TUM/DEN

(6) 1995TUM/DEN

2002REE/KAS

(continued)

BDEs The broken bonds

(boldface = (boldface =

recommended data; dissociated atom)

references in parentheses) Methods

∆fHo(R), kcal/mol (references in (kJ/mol) kcal/mol kJ/mol parentheses) References

spiropentane

∆fHo(R) = 91.0±1.0 (380.7±4.2)

1,3-cyclohexadiene

∆fHo(R) = 47.6 (199.2)

1,4-cyclohexadiene, substituted

∆fHo(R) = 48.2±1.2 (201.7±5.0)

X = H

X = Me

cyclohexene, substituted

98.8±1.0

(1) 73±5 (2) 73.2 (3) 74.3 (4) 74.3 (5) 79.1

(1) 70 (2) 76.0±1.2 (3) 73±2 (4) 77 (5) 75.0

(5) 80.4

413.4±4.2

305.4 306.3 310.9 310.9 331.1

292.9 318.0±5.0 305.4±8.4 322.2 313.7

336.4

Polanyi correlation

(1) Review (2) Kinetics (3) VLPP (4) PAC (5) Correlation

(1) Pyrolysis (2) SPST (3) PAC (4) PAC (5) Correlation

1971FER/WHI

(1) 1982MCM/GOL (2) 1985DEA (3) 1991STE/BRO (4) 1997LAA/MUL (5) 2001TUM/DEN

(1) 1968JAM/SUA (2) 1986TSA (3) 1989GRI/WAY (4) 1999CIR/KOR (5) 2001TUM/DEN

f X = H X’ = H

X = Me X’ = H

cyclohexene, substituted

cyclohexane, substituted

∆fHo(R) = 18±1.5 (75.3±6.3) X = H

X = Me

X = Et

X = Ph

cyclohexane, substituted

(E)-1,4-Me2

(2) 81.6 (3) 81.0

(3) 79.5

78.0

(1) 96.2 (2) 99.5 (3) 96.4±0.6 (4) 98 (5) 97.6

(5) 94.3

(5) 94.5

(5) 81.7

(6) 85.2

93.9

97.4

93.9

93.2

93.7

94.8

341.4 338.9

332.7

326.2

402.5 416.3 403.3±2.5 410.0 408.4

394.6

395.4

341.8

356.4

392.9

407.5

392.9

389.9

392.0

396.6

(2) Correlation (3) Correlation

Correlation

(1) Kinetics (2) SPST (3) EPR (4) PAC (5) Correlation

(6) Correlation

Correlation

(2) 2000DEN/DEN (3) 2001TUM/DEN

2001TUM/DEN

(1) 1978APP/KLU (2) 1981TSA (3) 1982CAS/GRI (4) 1999CIR/KOR (5) 2001TUM/DEN

(6) 2000DEN/DEN

2001TUM/DEN

BDEs The broken bonds

(boldface = (boldface =

recommended data; dissociated atom)

references in parentheses) Methods

∆fHo(R), kcal/mol (references in (kJ/mol) kcal/mol kJ/mol parentheses) References

1,3,5-cycloheptatriene

∆fHo(R) = 68.2±3 (285.3±12.6)

1,3-cycloheptadiene

cycloheptene

cycloheptane, substituted

∆fHo(R) = 12.1±1.0 (50.6±4.2)

X = H

X = Me

X = Et

(1) 82.9±7

(2) 73±1 (3) 73±2 (4) 76.6±3 (5) 73.2±2

83.0

82.9

(1) 93.3

(2) 94.0 (3) 92.5±1 (4) 92.5±1 (5) 96.5

(5) 93.0

(5) 93.8

346.9±29.3

305.4±4.2 305.4±8.4 320.5±12.6 306.3±8.4

347.3

346.9

389.1±12.6

393.3 387.0±4.2 387.0±4.2 403.8

389.0

392.4

(1) Electron impact

(2) Pyrolysis (3) ICR (4) ICR (5) Review

Correlation

(1) Polanyi correlation

(2) Kinetics (3) Photobromin. (4) Review

(5) Correlation

(1) 1960HAR/HON

(2) 1969VIN/DAU (3) 1979BAR/SCO (4) 1980DEF/MCM (5) 1982MCM/GOL

2001TUM/DEN

(1) 1966KER

(2) 1970JON/WHI (3) 1971FER/WHI

(4) 1982MCM/GOL

(5) 2001TUM/DEN

∆fHo(R) = 32.6±2.5 (136.4±10.5)

quadricyclane

∆fHo(R) = 138.3±1.3 (578.6±5.4)

quadricyclane

∆fHo(R) = 140.4±1.3 (587.4±5.4)

norboradine

∆fHo(R) = 122.3±1.9 (511.7±7.9)

cubane

∆fHo(R) = 198.6±4

(1) 96.7±2.5 (2) 99.4

109.4±1.3

111.5±1.3

115.6±1.9

102±4

404.6±10.5 415.9

457.7±5.4

466.5±5.4

483.7±7.9

426.8±16.7

Iodination

Ion flow tube

GPA

(1) 1970ONE/BAG (2) 1971DAN/TIP

1996LEE/DEP

1997HAR/EMR

BDEs The broken bonds

(boldface = (boldface =

recommended data; dissociated atom)

references in parentheses) Methods

∆fHo(R), kcal/mol (references in (kJ/mol) kcal/mol kJ/mol parentheses) References

bicyclooctane

∆fHo(R) = 22.0 (92.0)

cyclooctadiene

cyclooctene

cyclooctane, substituted

X = H

X = Me

X = Et

spiro[2.5]-octa-4,6-diene

cyclononane

97.7

79.3

85.4

95.7

94.4

93.7

70.7

96.3

408.8

331.8

357.2

400.2

395.0

392.2

295.6

403.9

Kinetics

Correlation

1971DAN/TIP

2001TUM/DEN

∆fHo(R, at 1 site) = 12.3 (51.5)

∆fHo(R, at 2 site) = 14.8 (61.9)

cyclodecane cyclo-C10H19-H

cycloundecane cyclo-C11H21-H

cyclododecane cyclo-C12H23-H

(Z)-decalin

(E)-decalin

(Z)-pinane

(1) 97.0 (2) 96.2 (3) 98.5 (4) 93.0

(2) 100.2 (3) 98.5 (3) 98.4

96.7

98.0

93.5

95.6

90.2

405.8 402.5 412.0

419.2 412.0 411.7

404.5

404.7

410.0

391.1

400.0

377.4

(1) Kinetics (2) AP (3) Correlation (4) Derived

(5) Photoelectr. spectroscopy

Correlation

(1) 1971DAN/TIP (2) 1998AUB/HOL (3) 2001TUM/DEN (4) 2001MAT/LEB

(5) 1986KRU/BEA

2001TUM/DEN

Table 3.4 C-H BDEs in Aromatic Hydrocarbons

BDEs The broken bonds

(boldface = recommended (boldface =

data; references dissociated atom)

in parentheses) Methods

∆fHo(R), kcal/mol (references in (kJ/mol) kcal/mol kJ/mol parentheses) References

benzene

∆fHo(R) = 78.9±0.8 (330.1±3.3)

phenyl

C-H at site 2

C-H at site 3

C-H at site 4

benzene, substituted

Y = 2-C(O)O-

Y = 3-C(O)O-

Y = 4-C(O)O-

Y = 2-C(O)OH Y = ∆fHo(R) = –7.9 (–33.1)

Y = 3-C(O)OH Y = ∆fHo(R) = –8.4 (–35.1)

(1) 112.3±1 (2) 111.2±0.8

(3) 113.5±0.5 (4) 113.3±2 (5) 112.9±0.5

79.9±3.1

95.3±3.2

110.6±3.4

113.9

110.4

112.3

114.5

114.0

469.9±4.2 465.3±3.3

474.9±2.1 474± 8 472.2± 2.2

334.3

398.7

462.8±14.2

476.6

461.9

469.9

479.1

477.0

(1) Iodination (2) GPA,

recommend. (3) Ion flow tube (4) Recommend. (5) GPA, revised

CID

Correlation

(1) 1967ROD/GOL (2) 1994BER/ELL

(3) 1995DAV/BIE (4) 1996TSA (5) 2002ERV/DET

1994WEN/SQU

1998NAS/SQU

Y = ∆fHo(R) = –8.6 (–36.0)

toluene

∆fHo(R) = 48.4±1.5 (202.5±6.3)

toluene, substituted

Y = 3-F

Y = 4-F

Y = 3-Cl

Y = 4-Cl

Y = 3-Br

Y = 4-Br

Y = 2-CH3

Y = 3-CH3

Y = 4-CH3

Y = 4-Et

Y = 2-Pr

Y = 3-Pr

Y = 4-Pr

Y = 4-tBu

Y = 3-CN

Y = 4-CN

(1) 87.9±1.5 (2) 88.1±2.2 (3) 88.6 (4) 88.5±1.5 (5) 89.6±1.0

(2) 89.3

(2) 89.7

(2) 89.1

(2) 88.7

(2) 89.7

(3) 90.8

(1) 87.3 (2) 89.6

(1) 87.8 (2) 88.8

(1) 87.7 (2) 88.4

(3) 87.0

(3) 87.6

(3) 86.8

(3) 87.0

(2) 89.4

(3) 88.7

(3) 88.0

367.8±6.3 368.6±9.2 370.7 370.3±6.3 375± 4

373.6

375.1

373.0

371.3

375.4

380.1

365.3 375.0

367.4 371.4

366.9 369.7

363.9

366.6

363.2

363.9

374.1

371.0

368.0

(1) VLPP (2) ICR (3) SPST (4) Recommend. (5) Recommend.