Handbook_of_Bond_Dissociation_Energies/Handbook of Bond Dissociation Energies/1589_CH01.PDFchapter one

Introduction

1.1A database of the BDEsChemistry and biochemistry are based on the concept of chemical bonds. The breakingand making of chemical bonds are involved in most chemical reactions. Chemists, bio-chemists, and chemical engineers thus need a complete database of the experimental dataof bond dissociation energies (BDEs).

This book contains the experimental BDE data of 2700 bonds in 2400 organic com-pounds. It is the first comprehensive book on experimental BDE data. It is very helpful toend users searching for BDE data.

1.2What is the BDE?The homolytic BDE is defined as the enthalpy change in the following fission:

RX R + X (1.1)

The BDE, DHo(RX), of an RX bond is derived in the usual way from heats of formationof the species involved in the previous reaction:

DHo(RX) = fHo(R) + fHo(X) fHo(RX) (1.2)

Here fHo represents the heats of formation of the respective species in the ideal gas stateat standard pressure and a reference temperature of 298.15 K. The BDE is also called thebond dissociation enthalpy.

Today, heats of formation, fHo(RX), of about four thousand organic compoundsare known. Most of them are available in the following publications: 1994FRE/KAB,1994PED, 1994GUR/VEY, 1989COX/WAG, 1988LIA/BAR, 1986PED/NAY, and http://webbook.nist.gov. The experimental uncertainty of heats of formation of organic com-pounds is generally within the chemical accuracy (1 kcal/mol, 1 calorie = 4.184 joules).From Equation 1.2, measurements of BDEs are equivalent to measurements of heats offormation of free radicals, and vice versa. Experimental BDEs can be determined directly,and can be derived from Equation 1.2. For example, we may derive the BDE values ofCH3X and C2H5X, where X = H, F, Cl, Br, I, OH, SH, NH2, CN, NO, NO2, CH3, and C2H5,if fHo(CH3) and fHo(C2H5) are known.

The number of organic compounds confirmed is about twenty million. We must esti-mate the heats of formation of organic compounds and BDEs using ab initio MO theory,

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density functional theory (DFT), semiempirical methods (such as PM3, AM1), molecularmechanics, group additivity, and others. The theoretical calculations are very interesting,but calculated BDEs are not included in this book.

1.3Why we need reliable BDEsThe BDE measurements of organic compounds started in the 1930s. Szwarc first summa-rized many experimental BDEs in organic compounds (1950SZW). The earlier experimen-tal data were collected by several publications: 1946STE, 1958COT, 1958SEM, 1962MOR,and 1966VED/GUR. Since then, almost all of these data have been updated. For example,the HC BDE value in benzene increases to 111.2 0.8 kcal/mol (1994BER/ELL) from102 kcal/mol (1966VED/GUR).

The equilibrium constant Keq is very sensitive to any error in the BDEs. An error of1, 2, or 3 kcal leads to an error of a factor of 5.4, 29.2, or 158, respectively, in the equilibriumconstant Keq at 298 K! The currently experimental uncertainty of the absolute majority ofBDE data is within 1 to 2 kcal/mol, which means the uncertainty is more than chemicalaccuracy (1 kcal/mol). Experimental BDE values thus will continue to be a source oflively controversy among scientists now and in the foreseeable future.

Several senior reviewers made efforts to update known BDEs as soon aas possible,such as 1966KER, 1969GOL/BEN, 1970ONE/BEN, 1978BEN, 1982MCM/GOL, 1988COL,1994BER/ELL, 1996TSA, and 1999COH. However, the number of experimental BDEs isincreasing sharply. For example, the CRC Handbook of Chemistry and Physics (2002CRC) col-lected the BDEs of about 400 bonds in organic compounds. Now we have collected experi-mental data for more than 2700 bonds. Chemists, biochemists, and chemical engineersneed a new publication which completely compiles the BDEs available.

By the way, a good BDE database of diatomic molecules can be found in Section 9 ofthe CRC Handbook of Chemistry and Physics (2002CRC), which collects over 800 data.BDEs of diatomic and smaller molecules can also be derived by using the NIST-JANAFThermochemical Table (1998CHA).

1.4Scope of this bookExperimental BDEs of many important organic compounds have been remeasured manytimes. A typical example is CH BDE in methane. It has been reported up to 50 times sincethe 1930s, and the value spreads from an early 98 kcal/mol to the current 105 kcal/mol.We have collected all experimental data; however, it is not necessary to copy all of thedata into this book, because most users are concerned with reliable experimentalvalues only.

This book will present recent experimental data for the given bonds, a maximum offive values for each bond. Which is the most reliable or best data for the BDEs? It is hardto answer this question. Recent measurements are likely to be more reliable generally.Readers may search more experimental data by using the references listed.

The BDEs have been tabulated based on the center atom in the radicals. They are dis-tinguished by CX, OX, NX, SX, SiX, GeX, SnX, PX, and SeX BDEs, and are organ-ized in Chapters Three through Nine.

The BDE data in some but not all inorganic compounds are listed in Chapter Ten. Atpresent, this book does not collect the BDE data in metallorganic compounds. A greatnumber of experimental data for ionic species are beyond the scope of this book, because

2 Handbook of Bond Dissociation Energies in Organic Compounds

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Chapter One:Introduction 3

these data have been available in other databases: 1988LIA/BAR and http://webbook.nist.gov.

1.5On energy unitsThe SI unit of energy is joule (1 calorie = 4.184 joules). There are three options for energyunits: (1) joule only, (2) calories only, and (3) both units. Using both units is a better choice.

Why? There are two reasons: (1) most heats of formation of radicals and BDEs used tobe measured in kcal/mol and (2) the range of the BDE values for common organic speciesis from about 40 (as ROOR) to 110 (as HC6H5, HC2H3) kcal/mol. As you know, a lowernumber is easy to remember in everyday life; it is the same in science. For example, wemay easily remember 105.0 kcal/mol of HCH3 BDE rather than 439.3 kJ/mol.

1.6How to search for BDEs in this bookWe encountered a great number of experimental BDEs from over 1000 publications. Thedata are like goods in a large department store: they should be organized on differentshelves or locations for our shopping. In this book, these data are managed in variouscategories. The chemical bonds with most similar structural environments are assembledin tables: goods shelves. There are 49 tables for BDE data in this book. All tabulatedvalues of the BDEs are systematized by the following seven orders:

1. Bond class, such as CH, CC, CO, CN, CS, CF, CCl, CBr, CI, and so on.2. Heteroatom(s) and functional group(s) at -position (relative to the broken

bond), such as O, CO, C(O)O, N, CN, NO, NO2, NN, S, SO, SO2, and more. Theheteroatom(s) and functional group(s) have significant influence on the BDEs.Organic chemistry is usually organized by the concept of functional groups.Therefore, users must first figure out heteroatom(s) and functional group(s) beforesearching the data. For example: The primary CH BDE in C6H5CH2H is listed in Table 3.4. In this book, the

boldface emphasizes the dissociated atom or group. The secondary CH BDE in PhCH2COCH3 is listed in Table 3.6.1. There is a CO

group at the -position of the CH bond. The secondary CH BDE in PhCOCH2NMe2 is listed in Table 3.6.3. There are a

CO group and an N atom at the -position of the CH bond. The secondary CH BDE in PhCOCH2SO2Ph is listed in Table 3.6.4. There are a

CO group and a SO2 group at the -position of the CH bond.3. Bond order (triple, double, and single) and the bond degree (primary, secondary,

or tertiary). The compounds with triple bond and primary BDEs are listed first.4. Saturated or unsaturated compounds. Saturated ones are listed first.5. Molecular size. The BDEs of smaller molecules are arranged first.6. Molecular shape (chain or cyclic). The BDEs of chain molecules are arranged first.7. While substituent(s)-containing, please first search the bonds in the parent

molecules. For example, the CH BDEs in substituted toluene are listed underC6H5CH2H.

Two indexes may also help your search, one of compound classes and the other ofcompound names.

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4 Handbook of Bond Dissociation Energies in Organic Compounds

1.7How to use the tables of the BDE dataAll BDE data are filed into 49 different tables. How can you find the BDEs? Let us see afirst example, the CH BDE in methane:

The first column in this table shows the broken bonds. The boldface emphasizes thedissociated atom or group; here the H is boldfaced. For example, CH3CH2CH2CH3 showsa secondary CH bond in n-butane is broken; (CH3CH2)3N shows a secondary CH bondin triethylamine is broken. All expressions are similar. The heat of formation of free radi-cals is shown in this cell. Chapter Eleven includes tables of all fHo(R).

The second column shows the experimental values of BDEs for the given bond. Thenumbers (1), (2), (3), (4), and (5) show five different resources or references. The recom-mended value is emphasized by boldface.

The third column shows various experimental methods for the relevant BDE value.For an explanation of terms, see the Notations and Abbreviations list in this book.

The fourth column shows the references for the given experimental methods and forthe relevant BDE value. A maximum of five values are provided. This is sufficient for mostusers. Readers can search for more references while using the references here.

Following are another three examples:

1. The CO BDE in methoxybenzene or anisole. The experimental data of BDE(CO)are from four different methods. The first three values are contributed from inde-pendent measurements of different research groups. The last one is derived byEquation 1.2, in which heats of formation of the parent molecules are taken fromthe given reference, and heats of formation of atoms and radicals are taken fromChapter Eleven.

2. The weakest HO BDEs in four tocopherols (vitamin E). They emphasize thedifference of experimental HO BDEs in gas phase and in liquid phase.

3. The HN BDEs in substituted diphenylamine. They show the effect of variousremote substituents Y on the HN BDEs.

BDEsThe 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

methane

CH3H

fHo(R) = 35.060.1(146.690.4)

(1) 105.00.1(2) 105.30.7(3) 104.80.2

(4) 105.30.6

(5) 104.990.03

439.30.4440.62.9438.50.8

440.62.5

439.280.13

(1) 1987DOB/BEN(2) 1988RUS/SEE(b)(3) 1988RUS/SEE

(4) 1991NIC/DIJ

(5) 1999RUS/LIT

(1) VLPP(2) PIMS detection(3) Spectrometric

detection(4) Resonance

detection(5) AE, revised

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BDEs(boldface =

recommended data;The broken bonds

references in parentheses)Methods

(boldface = (references indissociated group) kcal/mol kJ/mol parentheses) References

Chapter One:Introduction 5

methoxybenzene or anisole

CH3OC6H5

-tocopherol

R5 = R7 = CH3 (vitamin E)

-tocopherolR5 = R7 = H

-tocopherolR5 = CH3, R7 = H

-tocopherolR5 = H, R7 = CH3

diphenylamine, substituted

(1) 64.8(2) 65.2

(3) 65.3(4) 64.21.7

(1) 80.4

(2) 78.9(3) 78.9(4) 80.9 1.0,

in solution(5) 79.3, in

solution(5) 77.3, in

gas(5) 82.2, in

solution(5) 80.2, in

gas(6) 81.9

(6) 80.2

(6) 80.1

271.1272.8

273.2268.67.1

336.4

330.1330.1338.54.2

331.8

323.4

343.9

335.6

342.8

335.6

335.1

(1) VLPP(2) Tubular flow

reactor(3) VLPP(4) Derived from

fHo in ref.

(1) Estimated byrate constants

(2) EPR(3) EPR(4) AOP

(5) APC

(6) Correlation

(1) 1989SUR/KAF(2) 1993ARE/LOU

(3) 2001PRA/HEE(4) 1986PED/NAY

(1) 1985BUR/DOB

(2) 1992JAC/HOS(3) 1994LUC/PED(4) 1996BOR/LIU

(5) 1996WAY/LUS

(6) 2000DEN/DEN

H

O

R7

R5

3H

CH3

CH2CH2CHCH2CH2

CH3CH3

O

N

H

Y Y

(continued)

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BDEs(boldface =

recommended data;The broken bonds

references in parentheses)Methods

(boldface (references indissociated group) kcal/mol kJ/mol parentheses) References

6 Handbook of Bond Dissociation Energies in Organic Compounds

Y = p-Br

Y = p-MeO

Y = p-Me

Y = p-tBu

Y = p-N(CH3)2

(1) 88.1(2) 87.0

(1) 84.2(2) 83.3(4) 81.8

(2) 85.4(3) 86.3 in sol.

(3) 86.2 ingas

(4) 83.3

(2) 85.8

(4) 79.5

368.6364.2

352.3348.6342.2

357.5361.1 insol.360.7 ingas348.5

358.8

332.6

(1) AOP(2) Correlation

(3) PAC

(4) EPR

(1) 1993BOR/ZHA(2) 2000DEN/DEN

(3) 1997MAC/WAY

(4) 2002PRA/DIL

Table (continued)

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HANDBOOK OF BOND DISSOCIATION ENERGIES IN ORGANIC COMPOUNDSTable of ContentsChapter 01: Introduction1.1 A database of the BDEs1.2 What is the BDE?1.3 Why we need reliable BDEs1.4 Scope of this book1.5 On energy units1.6 How to search for BDEs in this book1.7 How to use the tables of the BDE data

Handbook_of_Bond_Dissociation_Energies/Handbook of Bond Dissociation Energies/1589_CH02.PDFchapter two

Experimental methodsfor measuring BDEs

The object of most end users is to find reliable data. However, it is very helpful if the usersknow the sources of experimental BDE data.

A very concise description of experimental methods is summarized below. It pro-vides main methods, measured quantities, applications, and references. It is hoped that itmay help the reader to better interpret the tables of BDE data from Chapters Threethrough Ten.

Spectrometry

Pyrolysis kinetics,including

Toluene carriertech

Very low pressurepyrolysis (VLPP)

Shock tubes

Single-pulse shocktubes (SPST)

Laser-poweredpyrolysis

Spacing of vibrationalenergy levels

Concentration of atoms,free radicals, andmolecules vs. time atdifferent temperatures,using various detectingtechniques, such as GC,HPLC, MS, FT-IR,UV/VIS, EPR, NMR,resonance fluorescence,chemiluminescence, etc.

Diatomicmolecules in gasphase

Species in gas andsolution phase

(1) 1968GAY(2) 1970DAR(3) 1979HUB/HER

1950SZW

(1) 1973GOL/SPO(2) 1979ROS/KIN(3) 1982MCM/GOL

(1) 1992DOU/MAC(2) 1997KIE/ZHA

(1) 1981TSA(2) 1999TSA

(1) 1982MCM/LEW(2) 1984LEW/GOL

Table 2.1 A Summary of Main Experimental Methods for Measuring BDEs

Experimental Methods Measured Quantities Applications References

(continued)

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Chemical equilibriumand kinetics

Photolysis, including

UV

Radiolysis

Laser

Photosensitized

Mass spectrometry(MS), including

Electron impact

Guided ion beam

High pressure

Concentration of atoms,free radicals, andmolecules at one orseveral temperatures,using various detectingmethods

Correlation betweenBDEs and rate constantsor activation energies

Concentration at one orseveral temperatures,using various analyticalmethods

Measure the givenquantities and describetheir correlation withBDEs

Ion intensities vs. electronenergy

Ion intensities vs. ionkinetic energy

Ion intensities vs.temperature

Species in gas andsolution phase

Species in gas andsolution phase

Species in gasphase

(1) 1966KER(2) 1977KER(3) 1982CAS/GRI(4) 1982MCM/GOL(5) 1984PAC/WIL(6) 1990KOE/SCO(7) 1990HAL(8) 1992WAL(9) 1994BER/ELL

(1) 1966KER(2) 1978KAT/RAJ(3) 2000DEN/DEN

(1) 1971LAU/OKA(2) 1995BOY/NOZ

(1) 1990LIN/SHE(2) 2001DAS

(1) 1987CHU/FOL(2) 1988PEN/CAO(3) 1997BEC/CAR

1967LOU/LAI

2001ERV

(1) 1979BER(2) 1984HOL/LOS(3) 1992HOL

(1) 1995ARM(2) 1998DET/ERV

(1) 1994BUS/KEM(2) 1994BOW(3) 1999MCM

Table 2.1 (continued) A Summary of Main Experimental Methods for Measuring BDEs

Experimental Methods Measured Quantities Applications References

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Ion cyclotronresonance (ICR)

High temperature

Photoionization(PIMS)

Pulsed highpressure

Kinetic method

Kineticenergy releasedistributions

Photospectrometry,including

Photoelectron

Electronphoto-detachment

Flowing afterglow

Collision-induced dissociation

Electrochemical,including acidities andoxidation potentials(AOP)

Photoacousticcalorimetry (PAC)

Ion intensities vs.time, vs. electron orphoton energy

Ion intensities vs.temperature

Ion intensities vs. photonenergy

Ion intensities at one orseveral temperatures

Ion intensities

Ion intensities vs. productkinetic energy

Measure the givenquantities and describetheir correlationwith BDEs

Electron count vs.electron kinetic energy

Ion intensities vs. photonenergy

Ion intensities vs. time, orvs. ion kinetic energy

Collision energy vs.cross section

Acidity, reversible redoxpotentials

Amplitude ofphotoacoustic signal andsolution transmittance

Time-resolved PAC

Species in gasphase

Species in solution

Species in solution

(1) 1980DEF/MCI(2) 2000BOR/ING(3) 1999ABB/NOT

1984MAR

(1) 1994BER/ELL(2) 1994BAR

(1) 1989MEO(2) 1993SHA/KEB

1994COO/PAT

1992BEA

(1) 1984MEA(2) 1994BER/ELL

(1) 1987WET/BRA(2) 1989CHE/ALB

(1) 1992SQU(2) 1994BER/ELL

(3) 1994WEN/SQU(4) 2001HAM/WEN

(1) 1993BOR/ZHA(2) 1993WAY/PAR(3) 1993ARN/FLO(4) 1995BOR/SAT

(1) 1989KAM/GIL(2) 1994PET(3) 1999LAA/MUL(4) 1999SAN/LAG(5) 2002SAN/MUR

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HANDBOOK OF BOND DISSOCIATION ENERGIES IN ORGANIC COMPOUNDSTable of ContentsChapter 02: Experimental methods for measuring BDEs

Handbook_of_Bond_Dissociation_Energies/Handbook of Bond Dissociation Energies/1589_CH03.PDFchapter three

Tabulated BDEs of CH bonds

3.1Chain saturated hydrocarbonsTable 3.1 C-H BDEs in Chain Saturated Hydrocarbons

BDEsThe 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

methaneCH3HfHo(R) = 35.060.1

(146.690.4)

ethaneCH3CH2HfHo(R) = 28.40.3

(118.81.3)

propaneCH3CH2CH2H

(1) 105.00.1(2) 105.30.7

(3) 104.80.2

(4) 105.30.6

(5) 104.990.03

(1) 100.50.5(2) 100.50.5

(3) 100.80.7

(4) 101.00.4

(5) 100.50.3

(1) 99.91.0(2) 99.82

439.30.4440.62.9

438.50.8

440.62.5

439.280.13

420.52.1420.52.1

421.72.9

422.61.7

420.51.3

418.04.2417.68.4

(1) VLPP(2) PIMS

detection(3) Spectrometric

detection(4) Resonance

fluorescencedetection

(5) AE, revised

(1) Kinetics(2) Resonance

fluorescencedetection

(3) PIMSdetection

(4) PIMSdetection

(5) VLPP

(1) Radical buffer(2) AE

(1) 1987DOB/BEN(2) 1988RUS/SEE(b)

(3) 1990SEE/RUS

(4) 1991NIC/DIJ

(5) 1999RUS/LIT

(1) 1984PAC/WIN(2) 1986BRO/LIG

(3) 1988RUS/SEE(b)

(4) 1992SEA/PIL

(5) 1997DOB/BEN

(1) 1982CAS/GRI(2) 1992HOL

(continued)

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Table 3.1 (continued) CH BDEs in Chain Saturated Hydrocarbons

12 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe 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

fHo(R) = 23.80.5(100 2)

propaneCH3CH2CH3fHo(R) = 21.00.7

(88 3)

butaneCH3CH2CH2CH2HfHo(R) = 18.60.5

(77.82.1)

butaneCH3CH2CH2CH3fHo(R) = 16.20.5

(67.82.1)

isobutane(CH3)2CHCH2H

(3) 100.90.5(4) 101.20.5

(1) 98.10.7

(2) 98.90.6

(3) 98.60.4

(4) 97.80.5

(5) 97.41.0

(1) 1012

(2) 100.2(3) 100.7(4) 101.7 0.5

(1) 99.10.4

(2) 98.30.5

(3) 98.60.5(4) 98.30.5(5) 97.41.0

(1) 100.21(2) 99.32

422.22.1423.42.1

410.52.9

413.82.5

412.51.7

409.22.1

407.54.2

422.68.4

419.2421.3425.52.1

414.61.7

411.12.2

412.52.1411.32.1407.54.2

419.24.2415.58.4

(3) SPST(4) PIMS

detection

(1) PIMSdetection

(2) PIMSdetection

(3) PIMSdetection

(4) PIMSdetection

(5) SPST

(1) Electronimpact

(2) AE(3) SPST(4) PIMS

detection

(1) PIMSdetection

(2) Resonancefluorescencedetection

(3) Review(4) PIMS(5) SPST

(1) Exp. analysis(2) AE

(3) 1996TSA(4) 1997SEE/SLA

(1) 1988RUS/SEE(b)

(2) 1990SEE/RUS

(3) 1992SEA/PIL

(4) 1997SEE/SLA

(5) 1999TSA

(1) 1958COT

(2) 1988HOL/LOS(3) 1990WAL/TSA(4) 1997SEE/SLA

(1) 1990SEE/RUS

(2) 1992SEA/PIL

(3) 1996TSA(4) 1997SEE/SLA(5) 1999TSA

(1) 1976BEN(2) 1992HOL

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Chapter Three:Tabulated BDEs of CH Bonds 13

fHo(R) = 16.71.0(704)

isobutane(CH3)3CHfHo(R) = 11.50.7

(483)

neopentane(CH3)3CCH2HfHo(R) = 8.72

(36.48.2)

2-methylbutane(CH3CH2)CH(CH3)2fHo(R) = 7

(29)

pentanenC5H11HfHo(R) = 13

(54.4)

pentaneCH3CH2(CH2)2CH3fHo(R) = 12

(50.2)

(3) 101.60.5

(4) 100.91

(1) 95.60.7(2) 95.0(3) 95.50.7

(4) 95.50.3

(5) 95.70.7

(1) 99.41

(2) 100.31(3) 99.41(4) 101.02(5) 101.1

(1) 91.62(2) 96.51(3) 92.6

(4) 95.8

100.2

99.2

425.12.1

422.04.2

400.02.9397.5399.62.9

399.61.3

400.42.9

415.94.2

419.74.2415.94.2422.68.4423

383.38.4403.84.2387.4

400.8

419.2

415.1

(3) PIMSdetection

(4) SPST

(1) SPST(2) VLPP(3) Resonance

fluorescencedetection

(4) Resonancefluorescencedetection

(5) Recommend.

(1) Polanyicorrelation

(2) Kinetics(3) SPST(4) Review(5) Laser flash

photolysis

(1) SPST(2) SPST(3) Photoelectron

spectroscopy(4) SPST

Derived fromfHo in ref.

Derived fromfHo in ref.

(3) 1997SEE/SLA

(4) 1999TSA

(1) 1985TSA(2) 1987BEN/KON(3) 1991SEA/PIL

(4) 1992SEA/PIL

(5) 1996TSA

(1) 1966KER

(2) 1969LAR/HAR(3) 1969TSA(4) 1982MCM/GOL(5) 2001IMR/DOB

(1) 1969TSA(2) 1981TSA(3) 1986KRU/BEA

(4) 1999TSA

1986PED/NAY

1986PED/NAY

(continued)

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Table 3.1 (continued) CH BDEs in Chain Saturated Hydrocarbons

14 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe 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

2-methylpentane(C3H7)CH(CH3)2fHo(R) = 0.82

(3.38.2)

2,3-dimethylbutaneCH3CH(CH3)CH(CH3)2fHo(R) = 0.72.4

(3.110)

hexanenC6H13HfHo(R) = 8

(33.5)

hexaneCH3CH2(CH2)3CH3fHo(R) = 7

(29.3)

heptaneCH3CH2(CH2)4CH3fHo(R) = 2

(8.2)

94.72

95.43.1

99.0

98.0

98.0

396.28.4

399.213.0

414.2

410.0

410.0

Pyrolysis

Equilibriumstudy

Derived fromfHo in ref.

Derived fromfHo in ref.

Derived fromfHo in ref.

1983SER/GOR

2000KIR/KOR

1986PED/NAY

1986PED/NAY

1986PED/NAY

03-1589.qxd 11-11-02 8:43 PM Page 14

Copyright 2003 by CRC Press LLC

3.2Chain unsaturated hydrocarbons

Chapter Three:Tabulated BDEs of CH Bonds 15

acetyleneHCCHfHo(R) = 135.10.7

(565.32.9)

propyneCH3CCHfHo(R) = 121.03.0

(506.312.6)

diaicetyleneHCCCCH

propyneCHCCH2HfHo(R) = 81.01.0

(3394)

2-butyneCH3CCCH2HfHo(R) = 70.22

(293.78.4)

1-butyneHCCCH2CH3fHo(R) = 70.52.2

(295.09.2)

(1) 134.91.2(2) 132.90.7

(3) 133.10.7(3) 132.80.7(4) 133.30.1(5) 131.30.7

130.23.0at 0K

128.82.9at 0K

(1) 89.22.4(2) 87.22(3) 90.33(4) 88.91.0(5) 91.81.0

(1) 90.7(2) 87.42(3) 84.8

(1) 85.0(2) 87.3(3) 83.12.2(4) 82.9

564.45.0556.12.9

556.92.9556.62.9557.80.3549.42.9

544.812.6at 0K

539.012.0at 0K

373.210.0364.88.4377.812.6372.04.2384.14.2

379.5365.78.4354.8

355.6365.3347.79.2346.8

(1) AE(2) Photoelectric

detachment(3) GPA(3) Recommend.(4) Photolysis(5) Electron

affinity

Photoelectricspectroscopy

Ion beamtandem MS

(1) VLPP(2) AE(3) GPA(4) Recommend.(5) SPST

(1) SPST(2) VLPP(3) Correlation

(1) VLPP(2) SPST(3) Review(4) Correlation

(1) 1979BER(2) 1990ERV/GRO

(3) 1994BER/ELL

(4) 1994MOR/ASH(5) 2002KIR/TSC

1995ROB/POL

2000SHI/ERV

(1) 1979KIN/NGU(2) 1988HOL/POS(3) 1995ROB/POL(4) 1996TSA(5) 1999TSA

(1) 1978TSA(2) 1982NGU/KIN(3) 2000DEN/DEN

(1) 1981NGU/KIN(2) 1981TSA(3) 1982MCM/GOL(4) 2000DEN/DEN

(continued)

Table 3.2 CH BDEs in Chain Unsaturated Hydrocarbons

BDEsThe 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

03-1589.qxd 11-11-02 8:43 PM Page 15

Copyright 2003 by CRC Press LLC

Table 3.2 (continued) CH BDEs in Chain Unsaturated Hydrocarbons

16 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe 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-penten-3-yneCH2=CHCCCH2HfHo(R) = 84.0

(351.5)

2-pentyneCH3CCCH2CH3fHo(R) = 65.22.2

(272.89.2)

1-pentyneHCCCH2CH2CH3fHo(R) = 66.22

(277.08.4)

3-methyl-1-butyneHCCCH(CH3)2fHo(R) = 61.52.2

(257.39.2)

4-methyl-2-pentyneCH3CCCH(CH3)2fHo(R) = 53.02.2

(221.89.2)

5-decyneCH3(CH2)3CCCH2(CH2)2CH3

ethyleneH2C=CHHfHo(R) = 71.60.8

(299.63.3)

86.8

87.32.3

83.62

(1) 82.52(2) 81.02.3

82.32.7

83.2

(1) 111.12.2(2) 110.12(3) 110.22(4) 111.20.8

363.3

365.39.6

349.88.4

345.28.4338.99.6

344.311.3

348.0

464.89.2460.78.4461.18.4465.33.3

VLPP

VLPP

AE

(1) AE(2) VLPP

VLPP

Correlation

(1) ICR(2) Kinetics(3) Review(4) Recommend.

1992STA/KIN

1981KIN/NGU

1976LOS/TRA

(1) 1976LOS/TRA(2) 1977KIN

1981KIN/NGU

2001TUM/DEN

(1) 1980DEF/MCI(2) 1981STE/ROW(3) 1982MCM/GOL(4) 1994BER/ELL

03-1589.qxd 11-11-02 8:43 PM Page 16

Copyright 2003 by CRC Press LLC

Chapter Three:Tabulated BDEs of CH Bonds 17

alleneCH2=C=CHHfHo(R) = 81.01

(338.94)

propeneCH3CH=CHHfHo(R) = 63.81.5

(266.96)

propeneCH2=CHCH2HfHo(R) = 40.80.7

(1713)

(Z)-2-butene(Z)-CH3CH=CHCH2HfHo(R) = 34.92

(1468)

(E)-2-butene(E)-CH3CH=CHCH2H

1-buteneCH2=CHCH2CH2HfHo(R) = 46.0

(192.5)

1-buteneCH2=CHCH2CH3

(5) 110.20.4

(1) 92.41.2(2) 88.73

(1) 1092.4(2) 111.1

(1) 86.71.5(2) 87.20.5

(3) 88.80.4(4) 88.20.7(5) 87.01.1

(1) 89.7(2) 85.0

85.3

98.1

(1) 82.3(2) 81.51.5(3) 82.61.3

461.11.3

386.65.0371.112.6

456.110.0464.8

362.86.3364.82.1

371.51.7368.62.9364.04.6

375.3355.8

356.8

410.5

344.3341.06.3345.65.4

(5) FT-IR-GCdetection

(1) Kinetics(2) GPA

SPST

(1) VLPP(2) Pulse shock

tube(3) GPA(4) Recommend.(5) PIMS detection

(1) SPST(2) Correlation

Correlation

Photoelectronspectroscopy

(1) SPST(2) Pyrolysis(3) Review

(5) 1996KAI/WAL

(1) 1971WAL(2) 1995ROB/POL

(1) 1988CUI/HE(2) 1999TSA

(1) 1979ROS/KIN(2) 1991ROT/BAU

(3) 1996ELL/DAV(4) 1996TSA(5) 1997SEE/SLA

(1) 1999TSA(2) 2000DEN/DEN

2000DEN/DEN

1984SCH/HOU

(1) 1969TSA(2) 1970TRE(3) 1982MCM/GOL

(continued)

03-1589.qxd 11-11-02 8:43 PM Page 17

Copyright 2003 by CRC Press LLC

Table 3.2 (continued) CH BDEs in Chain Unsaturated Hydrocarbons

18 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe 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

fHo(R) = 31.81.5(133.16.3)

isobuteneCH2=C(CH3)CH2HfHo(R) = 30.60.6

(128.02.5)

1,3-pentadieneCH2 = CHCH = CHCH2HfHo(R) = 493

(20512.6)

2,3-pentadieneCH3CH=C=CHCH2H

1,4-pentadiene(CH2=CH)2CHHfHo(R) = 49.71.0

(207.94.2)

1-penteneCH2=CHCH2CH2CH3fHo(R) = 26.22

(109.68.4)

2-methyl-1-buteneCH2=C(CH3)CH2CH3

3-methyl-1-buteneCH2=CHCH(CH3)2

(4) 83.8

(5) 83.5

(1) 86.21(2) 86.70.6(3) 89.1(4) 85.5

(1) 79.81.0(2) 79.71.0(3) 83.03

87.3

(1) 79.51.7(2) 76.4(3) 76.61.0(3) 76.61.0

(1) 82.52(2) 83.4

83.0

(1) 79.51.7(2) 76.4

350.6

349.2

360.74.2362.82.5372.8357.6

333.94.2333.54.2347.312.6

365.0

332.67.1319.7320.54.2320.54.2

345.28.4348.8

347.3

332.67.1319.7

(4) Protonaffinity

(5) Correlation

(1) Pyrolysis(2) Shock tube(3) SPST(4) Correlation

(1) Iodination(2) Pyrolysis(3) Review

Correlation

(1) Isomerization(2) Pyrolysis(3) PAC(3) AE

(1) AE(2) Correlation

Correlation

(1) Isomerization(2) Pyrolysis

(4) 1987LIA/AUS

(5) 2001TUM/DEN

(1) 1977TRE/WRI(2) 1991ROT/BAU(3) 1999TSA(4) 2001TUM/DEN

(1) 1973ONE/BEN(2) 1980TRE(3) 1982MCM/GOL

2000DEN/DEN

(1) 1970EGG/JOL(2) 1982TRE(3) 1991CLA/CUL

(1) 1976LOS/TRA(2) 2000DEN/DEN

2000DEN/DEN

(1) 1970EGG/JOL(2) 1982TRE

03-1589.qxd 11-11-02 8:43 PM Page 18

Copyright 2003 by CRC Press LLC

Chapter Three:Tabulated BDEs of CH Bonds 19

fHo(R) = 20.82(87.08.4)

3-methyl-2-buteneCH3CH=C(CH3)CH2H

2-ethyl-1-propeneCH2=C(CH3CH2)CH2HfHo(R) = 26.22

(109.68.4)

(E)-2-pentene(E)-CH3CH=CHCH2CH3

(Z)-2-pentene(Z)-CH3CH=CHCH2CH3

1-hexeneCH2=CHCH(CH2)2CH3

3-methyl-1,4-pentadiene(CH2=CH)2C(CH3)HfHo(R) = 46.3

(202.0)

(Z)-4-methyl-2-pentene(Z)-(CH3)2CHCH=CHCH3

4-methyl-3-pentene(CH3)2C=CHCH2CH3

(3) 83.1

(4) 81.2

84.2

85.12

(1) 81.71.5

(2) 82.5

(1) 80.61.5

(2) 82.6

83.4

77

79.8

79.3

347.7

339.6

352.4

356.18.4

341.86.3

345.2

337.2

345.4

348.8

322.2

333.9

331.9

(3) Reanalysis ofpyrolysis data

(4) Correlation

Correlation

AE

(1) Derived fromfHo in ref.

(2) Correlation

(1) Derived fromfHo in ref.

(2) Correlation

Correlation

PAC

Correlation

Correlation

(3) 1998BRO/BEC

(4) 2000DEN/DEN

2000DEN/DEN

1976LOS/TRA

(1) 1986PED/NAY

(2) 2000DEN/DEN

(1) 1986PED/NAY

(2) 2000DEN/DEN

2001TUM/DEN

1999LAA/MUL

2001TUM/DEN

2001TUM/DEN

(continued)

03-1589.qxd 11-11-02 8:43 PM Page 19

Copyright 2003 by CRC Press LLC

Table 3.2 (continued) CH BDEs in Chain Unsaturated Hydrocarbons

20 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe 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

2,3-dimethyl-2-butene(CH3)2C=C(CH3)CH2HfHo(R) = 9.51.5

(39.76.3)

2,3-dimethy-1-buteneCH2=C(CH3)CH(CH3)2fHo(R) = 91.5

(37.76.3)

(Z)-2,5-dimethyl-3-hexene(Z)-(CH3)2CHCH=CHCH(CH3)2

1,3-octedieneCH2=CHCH=CHCH2(CH2)2CH3

1-octeneCH2 = CHCH2(CH2)4CH3

(E)-2-octene(E)-CH3CH=CHCH2(CH2)3CH3

1,8-nonedieneCH2=CHCH2(CH2)4CH=CH2

Z,Z-2,8-decedieneCH3CH=CH(CH2)4CH=CHCH3

1-hexadeceneCH2=CHCH2(CH2)12CH3

(1) 78.01.0(2) 84.7

(1) 76.31.0(2) 84.3

80.3

79.3

83.4

81.9

83.6

81.6

83.4

326.44.2354.3

319.2352.8

336.1

332.0

348.9

342.7

349.8

341.6

348.8

(1) Iodination(2) Correlation

(1) Iodination(2) Correlation

Correlation

Correlation

Correlation

Correlation

Correlation

Correlation

Correlation

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

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

2001TUM/DEN

2001TUM/DEN

2000DEN/DEN

2000DEN/DEN

2001TUM/DEN

2001TUM/DEN

2001TUM/DEN

03-1589.qxd 11-11-02 8:43 PM Page 20

Copyright 2003 by CRC Press LLC

Chapter Three:Tabulated BDEs of CH Bonds 21

allyl triphenyl phosphoniumbromidePh3P

+CH2CH=CH2 Br

3-phenyl-allyl triphenylphosphonium bromidePh3P

+CH2CH=CHPh Br

85.9

81.0

359.4

338.9

AOP

AOP

1996ZHA/FRY

1996ZHA/FRY

BDEsThe 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 CH BDEs in Cyclic Hydrocarbons

cyclopropene

fHo(R) = 105.14.1(439.717.2)

cyclopropane

fHo(R) = 66.90.3(279.91.3)

methylcyclopropane

fHo(R) = 51.11.6(213.86.7)

90.44.0

(1) 1013

(2) 100.20.4(3) 106.30.25(4) 105.92.7(5) 102.5

97.41.6

378.312.6

422.612.6

419.31.7444.81.0443.111.3429.0

407.56.7

ICR

(1) Polanyicorrelation

(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)

H

H

H

H

CH2 H

3.3Cyclic hydrocarbons

03-1589.qxd 11-11-02 8:43 PM Page 21

Copyright 2003 by CRC Press LLC

Table 3.3 (continued) CH BDEs in Cyclic Hydrocarbons

22 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe 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) = 51.41.0(215.14.2)

6,6-dimethylfulvene

1,3-cyclopentadienes,substituted

1,3-cyclopentadienes,substituted

at 1 site HfHo(R) = 63.92.0

(267.48.4)at 1,4 site Ph2

(1) 953

(2) 96.5

(3) 96.81.0(4) 97.80.3(5) 100.0

84.5

86.52

(1) 82.92.2(2) 81.2(3) 83.90.5(4) 81.52.7(5) 82.51

(6) 75

397.512.6

403.8

405.04.2409.21.3418.5

353.5

361.98.4

346.99.2339.7351.02.1341.011.3345.24.2

313.8

(1) Polanyicorrelation

(2) Polanyicorrelation

(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

H

H

Me CH2 H

12

345

6

CH2 H

H1 234

5

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Chapter Three:Tabulated BDEs of CH Bonds 23

1,3-cyclopentadienes,substituted

R = MefHo(pentamethyl-cyclo-pentadienyl) = 16.11.0

(67.44.2)

Ph

cyclopentene

fHo(R) = 38.41.0(160.74.2)

cyclopentane, substituted

fHo(R) = 25.31.0(105.94.2)

X = H

X = Me

X = Et

X = Ph

3-tert-butylbicyclo[1.1.1]-pentane

(1) 77

(1) 78(2) 74.1

(1) 82.31(2) 822(3) 81.9

(1) 94.91(2) 95.02(3) 96.00.2(4) 95.61(5) 97.6

(5) 93.7

(5) 93.7

(6) 81.9

109.73.3

322.2

326.4310.0

344.34.2343.18.4342.5

397.14.2397.58.4401.70.8400.04.2408.5

392.2

392.3

342.7

459.013.8

(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)

HR

R

R

R

R

H

H

H

X

tBuH

03-1589.qxd 11-11-02 8:43 PM Page 23

Copyright 2003 by CRC Press LLC

Table 3.3 (continued) CH BDEs in Cyclic Hydrocarbons

24 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe 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) = 91.01.0(380.74.2)

1,3-cyclohexadiene

fHo(R) = 47.6(199.2)

1,4-cyclohexadiene,substituted

fHo(R) = 48.21.2(201.75.0)

X = H

X = Me

cyclohexene, substituted

98.81.0

(1) 735(2) 73.2(3) 74.3(4) 74.3(5) 79.1

(1) 70(2) 76.01.2(3) 732(4) 77(5) 75.0

(5) 80.4

413.44.2

305.4306.3310.9310.9331.1

292.9318.05.0305.48.4322.2313.7

336.4

Polanyicorrelation

(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

H

H

H

H

H

H

X

X

H

X

X

03-1589.qxd 11-11-02 8:44 PM Page 24

Copyright 2003 by CRC Press LLC

fHo(R) = 28.6 (119.7)X = H X = H

X = Me X = H

cyclohexene, substituted

cyclohexane, substituted

fHo(R) = 181.5 (75.36.3)X = H

X = Me

X = Et

X = CH=CH2

X = Ph

cyclohexane, substituted

(Z)-1,2-Me2

(E)-1,2-Me2

(Z)-1,3-Me2

(E)-1,3-Me2

(Z)-1,4-Me2

(E)-1,4-Me2

(1) 81.9(2) 81.6(3) 81.0

(3) 79.5

78.0

(1) 96.2(2) 99.5(3) 96.40.6(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

342.7341.4338.9

332.7

326.2

402.5416.3403.32.5410.0408.4

394.6

395.4

341.8

356.4

392.9

407.5

392.9

389.9

392.0

396.6

(1) AOP(2) Correlation(3) Correlation

Correlation

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

(6) Correlation

Correlation

(1) 1988BOR/CHE(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

(continued)

HH

Me Me

H

X

Z

E

Chapter Three:Tabulated BDEs of CH Bonds 25

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Table 3.3 (continued) CH BDEs in Cyclic Hydrocarbons

26 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe 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) = 68.23(285.312.6)

1,3-cycloheptadiene

cycloheptene

cycloheptane, substituted

fHo(R) = 12.11.0(50.64.2)

X = H

X = Me

X = Et

(1) 82.97

(2) 731(3) 732(4) 76.63(5) 73.22

83.0

82.9

(1) 93.3

(2) 94.0(3) 92.51(4) 92.51(5) 96.5

(5) 93.0

(5) 93.8

346.929.3

305.44.2305.48.4320.512.6306.38.4

347.3

346.9

389.112.6

393.3387.04.2387.04.2403.8

389.0

392.4

(1) Electronimpact

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

Correlation

Correlation

(1) Polanyicorrelation

(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

2001TUM/DEN

(1) 1966KER

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

(4) 1982MCM/GOL

(5) 2001TUM/DEN

H

H

HH

HH

HX

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Chapter Three:Tabulated BDEs of CH Bonds 27

norbornene

fHo(R) = 32.62.5(136.410.5)

quadricyclane

fHo(R) = 138.31.3(578.65.4)

quadricyclane

fHo(R) = 140.41.3(587.45.4)

norboradine

fHo(R) = 122.31.9(511.77.9)

cubane

fHo(R) = 198.64(830.916.7)

(1) 96.72.5(2) 99.4

109.41.3

111.51.3

115.61.9

1024

404.610.5415.9

457.75.4

466.55.4

483.77.9

426.816.7

Iodination

Ion flow tube

Ion flow tube

Ion flow tube

GPA

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

1996LEE/DEP

1996LEE/DEP

1996LEE/DEP

1997HAR/EMR

(continued)

H

12

3 4 5

6

7

H

12

3

45 6

7

75

3

1

H

24 6

HH

12

3 4 5

6

7

H

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Table 3.3 (continued) CH BDEs in Cyclic Hydrocarbons

28 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe 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

cyclononanecyclo-C9H17H

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

Correlation

Correlation

Correlation

Correlation

1971DAN/TIP

2001TUM/DEN

2001TUM/DEN

2001TUM/DEN

2001TUM/DEN

2001TUM/DEN

H

H

H

H

H

X

H

H H

03-1589.qxd 11-11-02 8:44 PM Page 28

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Chapter Three:Tabulated BDEs of CH Bonds 29

adamantane

fHo(R, at 1 site) = 12.3(51.5)

fHo(R, at 2 site) = 14.8(61.9)

cyclodecanecyclo-C10H19H

cycloundecanecyclo-C11H21H

cyclododecanecyclo-C12H23H

(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

96.7

98.0

93.5

95.6

90.2

405.8402.5412.0

419.2412.0411.7

404.5

404.7

410.0

391.1

400.0

377.4

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

(5) Photoelectr.spectroscopy

Correlation

Correlation

Correlation

Correlation

Correlation

Correlation

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

(5) 1986KRU/BEA

2001TUM/DEN

2001TUM/DEN

2001TUM/DEN

2001TUM/DEN

2001TUM/DEN

2001TUM/DEN

H

1 2

HH

HH

HMe

Me

Me

03-1589.qxd 11-11-02 8:44 PM Page 29

Copyright 2003 by CRC Press LLC

Table 3.4 CH BDEs in Aromatic Hydrocarbons

30 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe broken bonds

(boldface = recommended(boldface =

data; referencesdissociated atom)

in parentheses)Methods

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

benzene

fHo(R) = 78.90.8(330.13.3)

phenyl

CH at site 2

CH at site 3

CH at site 4

benzene, substituted

Y = 2-C(O)O

Y = 3-C(O)O

Y = 4-C(O)O

Y = 2-C(O)OHY = fHo(R) = 7.9 (33.1)

Y = 3-C(O)OHY = fHo(R) = 8.4 (35.1)

(1) 112.31(2) 111.20.8

(3) 113.50.5(4) 113.32(5) 112.90.5

79.93.1

95.33.2

110.63.4

113.9

110.4

112.3

114.5

114.0

469.94.2465.33.3

474.92.1474 8472.2 2.2

334.3

398.7

462.814.2

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

3.4Aromatic hydrocarbons

H

H

H

HH

H23

456 1

HY

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Chapter Three:Tabulated BDEs of CH Bonds 31

Y = 4-C(O)OHY = fHo(R) = 8.6 (36.0)

toluene

fHo(R) = 48.41.5(202.56.3)

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

113.8

(1) 87.91.5(2) 88.12.2(3) 88.6(4) 88.51.5(5) 89.61.0

(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

476.1

367.86.3368.69.2370.7370.36.3375 4

373.6

375.1

373.0

371.3

375.4

380.1

365.3375.0

367.4371.4

366.9369.7

363.9

366.6

363.2

363.9

374.1

371.0

368.0

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

(1) Photoelectr.spectroscopy

(2) Correlation

(3) Correlation

(1) 1979ROS/GOL(2) 1980DEF/MCI(3) 1990WAI/TSA(4) 1994BER/ELL(5) 1996TSA

(1) 1986HAY/KRU

(2) 2000DEN/DEN

(3) 2002KRO/TUM

(continued)

HCH2

HCH2Y

03-1589.qxd 11-11-02 8:44 PM Page 31

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Table 3.4 (continued) CH BDEs in Aromatic Hydrocarbons

32 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe broken bonds

(boldface = recommended(boldface =

data; referencesdissociated atom)

in parentheses)Methods

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

Y = 3-NO2

Y = 4-NO2

Y = 4-PhO

Y = 4-PhSO2

Y = 4-CH2OCH3

Y = 3-MeO

Y = 4-MeO

Y = 3-EtOC(O)

Y = 4-EtOC(O)

Y = 2,4-Cl2

Y = 3,4-Cl2

Y = 2,3-Me2

Y = 2,4-Me2

Y = 3,5-Me2

Y = 2,3,4,5,6-Me5

Y = 3-CH2

Y = 3,5-(CH2)

ethylbenzene, substituted

fHo(R) = 40.4(169.0)

Y = H

(3) 89.6

(2) 89.2(4) 86.5

(2) 89.7

(5) 88

(3) 85.4

(3) 90.5

(3) 86.6

(3) 89.1

(3) 89.4

(3) 88.6

(2) 88.3

(3) 89.5

(2) 89.1

(2) 89.5

(2) 88.6

(6) 90.72.9

(7) 88.25.0

(1) 84.6(2) 86.2

(3) 85.41.5(4) 90.3

(5) 87.0

375.0

373.4361.9

375.4

368.2

357.5

378.8

362.5

372.7

374.1

370.9

369.6

374.3

373.0

374.3

370.9

379.512.1

369.020.9

354.0360.7

357.36.3377.8

364.1

(4) AOP

(5) AOP

(6) CID

(7) CID

(1) VLPP(2) Proton

affinity(3) Review(4) Reanal. of

pyrolysisdata

(4) 1995BOR/ZHA(c)

(5) 1993ZHA/BOR

(6) 2000HAM/WEN

(7) 2001HAM/WEN

(1) 1981ROB/STE(2) 1982MEO

(3) 1982MCM/DOL(4) 1998BRO/BEC

(5) 2000DEN/DEN

YCH

H

CH3

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Chapter Three:Tabulated BDEs of CH Bonds 33

Y = p-C2H5

Y = p-Br

Y = p-tBu

Y = p-MeOC(O)

prop-2-enylbenzenePhCH2CH=CH2

n-propylbenzenePhCH2C2H5

i-propylbenzene, substituted

Y = 2,5-Me2

Y = 4-t-Bu

t-butylbenzeneC6H5C(CH3)2CH2H

(E)-1-phenylpropene(E)-Ph-CH=CH-CH2H

1-phenylcyclobutene

cyclopentylbenzene

(6) 86.3

(6) 87.1

(6) 86.5

(6) 87.0

84.4

(1) 86.1(2) 87.5

86.7

83.5

98.7

78.92.6

85.62.6

88.0

361.1

364.4

361.9

364.1

353.1

360.2366.2

362.8

349.3

413.0

330.110.9

358.210.9

268.2

(6) Correlation

(6) Correlation

Correlation

(1) Proton affinity(2) Correlation

Correlation

Correlation

FT-MS

FT-MS

Correlation

(6) 2002KRO/TUM

1995TUM/DEN

(1) 1982MEO(2) 2000DEN/DEN

2002KRO/TUM

2002KRO/TUM

2002GLA/MAK

2002GLA/MAK

2002KRO/TUM

(continued)

C(CH3)2

H

Y

H

H

12

34

5

67

8

9 10

H

03-1589.qxd 11-11-02 8:44 PM Page 33

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Table 3.4 (continued) CH BDEs in Aromatic Hydrocarbons

34 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe broken bonds

(boldface = recommended(boldface =

data; referencesdissociated atom)

in parentheses)Methods

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

cyclohexylbenzene

diphenylmethanePh2CH2fHo(R) = 72.21.0

(302.14.2)

diphenylmethane, substituted(p-PhC6H4)2CH2

1,2-diphenylethanePhCH2CH2Ph

2-phenylpropanePh(CH3)2CHfHo(R) = 32.01.0

(133.94.2)

1,1-diphenylethanePh2C(CH3)CH

85.2

(1) 842(2) 82(3) 84.50.5(4) 85.8

(5) 85.3

80

87.0

(1) 83.6(2) 84.41.5(3) 83.21(4) 87.3

(5) 84.8

(1) 812(2) 82.8

(3) 83.9

356.4

351.58.4343.1353.52.1359.0

356.9

334.7

364.1

349.8353.16.3348.14.2365.3

354.7

338.98.4346.4

351.0

Correlation

(1) VLPP(2) AOP(3) Electrochem.(4) Reanal. of

pyrolysis data(5) Correlation

AOP

Correlation

(1) VLPP(2) Review(3) PAC(4) Reanal. of

pyrolysis data(5) Correlation

(1) VLPP(2) Reanal. of

pyrolysis data(3) Correlation

2002KRO/TUM

(1) 1991STE/BRO(2) 1991BOR/CHE(3) 1991PAR/HAN(4) 1998BRO/BEC

(5) 2000DEN/DEN

1989BOR/HAR

2000DEN/DEN

(1) 1981ROB/STE(2) 1982MCM/GOL(3) 1997LAA/BOR(4) 1998BRO/BEC

(5) 2000DEN/DEN

(1) 1981STE(2) 1998BRO/BEC

(3) 2000DEN/DEN

H

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Chapter Three:Tabulated BDEs of CH Bonds 35

thiphenylmethane,substituted

fHo(Ph3C) = 93.72.0(392.08.4)

Y = p-H Y = p-H Y = p-H

Y = p-MeO p-MeO p-MeO

Y = p-MeO p-MeO pH

Y = p-Me p-Me p-Me

Y = p-MeO pH pH

Y = p-Me p-Me pH

Y = p-Me pH pH

Y = p-tBu p-tBu p-tBu

thiphenylmethane,substituted(pHC6F4)3CH

1,1,3,3-tetraphenylpropenePh2C=CHC(Ph)2H

1,1,3,5,5-pentaphenyl-1,4-pentadienePh2C=CHCH(Ph)CH=CPh2

benzocyclobutene

(1) 812(2) 80.83(3) 79.0(4) 82.7(5) 85.4

(3) 78.1

(3) 79.3

(3) 79.0

(3) 80.7

(3) 80.3

(3) 79.1

(3) 74.4

82.3

77

75.1

924

338.98.4338.112.6330.5346.0357.3

326.8

331.8

330.5

337.6

336.0

331.0

311.3

344.3

322.2

314.2

384.916.7

(1) AOP(2) AOP(3) AOP(4) Correlation(5) Correlation

AOP

AOP

AOP

FT-MS

(1) 1991PAR/HAN(2) 1993BOR/ZHA(b)(3) 1997ARN/FLO(4) 2000DEN/DEN(5) 2002KRO/TUM

1993BOR/ZHA(b)

1989BOR/HAR

1991BOR/CHE

2000GLA/MAK

(continued)

C

Y

Y

Y

H

HH

03-1589.qxd 11-11-02 8:44 PM Page 35

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Table 3.4 (continued) CH BDEs in Aromatic Hydrocarbons

36 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe broken bonds

(boldface = recommended(boldface =

data; referencesdissociated atom)

in parentheses)Methods

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

benzocyclobutadiene

indane

fHo(indanyl) = 48.82.0(204.28.4)

indene

fHo(indenyl) = 71(297.1)

indene, substituted

Y = 2-Br

Y = 3-Me

Y = 3-t-Bu

Y = 2-Ph

1144

85.9

(1) 843(2) 81.50.5(3) 81.12.4(4) 83.0

(5) 81.2

(1) 80.9

(1) 77.6

(1) 78.5

(1) 79.3(2) 843

477.016.7

359.4

351.512.6341.02.1339.310.0347.3

339.7

338.5

324.7

328.4

331.8351.512.6

FT-MS

Correlation

(1) Review(2) Electrochem.(3) ICR(4) Reanal. of

pyrolysis data(5) Correlation

(1) AOP

(2) VLPP

2000BRO/KAS(b)

2000DEN/DEN

(1) 1982MCM/GOL(2) 1991PAR/HAN(3) 1997ROM/JAN(4) 1998BRO/BEC

(5) 2001TUM/DEN

(1) 1992BOR/SAT

(2) 1981STE

H

HH

HH

12

3

45

67

H H

Y

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Chapter Three:Tabulated BDEs of CH Bonds 37

Y = 3-Ph

Y = 3-MeO

Y = 3-MeS

Y = 2-PhS

Y = 3-CN

Y = 3-c-C4H8N

Y = 2-c-C4H8N

Y = 3-c-C5H10N

Y = 2-c-C5H10N

Y = 3-c-OC4H8N

Y = 2-c-OC4H8N

Y = 2-(4-MeOC6H4)

Y = 2-(4-MeC6H4)

Y = 3-C(O)NH2

Y = 2-C(O)OMe

Y = 3-C(O)OMe

Y = 6-NO23-Me

Y = 1,2,3-Ph3

tetralin

fHo(R) = 371.2(154.85.0)

X = H X = H

X = Me X = H

X = Me X = Me

1,5,7-trimethyltetralin

(1) 75.3

(1) 76.4

(1) 74.1

(1) 80.2

(1) 77.9

(1) 70.3

(1) 83.5

(1) 72.3

(1) 82.5

(1) 73.4

(1) 82.8

(1) 79.3

(1) 79.1

(1) 77.7

(1) 79.2

(1) 77.6

(1) 78.4

(1) 75.8

(1) 82.91.2(2) 83.6(3) 82.6

(4) 79.3(3) 80.4

(4) 80.5

80.9

315.1

319.7

310.0

335.6

325.9

294.1

349.4

302.5

345.2

307.1

346.4

331.8

331.0

322.2

331.4

324.7

328.0

317.1

346.95.0349.6345.6

331.8336.4

336.8

338.4

(1) PAC(2) Correlation(3) Correlation

(4) Correlation

Correlation

(1) 1997LAA/MUL(2) 2000DEN/DEN(3) 2002KRO/TUM

(4) 1995TUM/DEN

2002KRO/TUM

(continued)

HXXH

H CH3

CH3

CH3

03-1589.qxd 11-11-02 8:44 PM Page 37

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Table 3.4 (continued) CH BDEs in Aromatic Hydrocarbons

38 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe broken bonds

(boldface = recommended(boldface =

data; referencesdissociated atom)

in parentheses)Methods

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

1,4-dihydronaphthalene

1,2-dihydronaphthalene

naphthalene

fHo(R) = 96.01.3(401.75.4)

naphthalene

fHo(R) = 95.71.4(400.45.9)

83.0

(1) 86.0

(2) 80.4

(1) 112.21.3(2) 113.45.2

(3) 112.83.3

(1) 111.91.4(2) 115.44.9

(3) 113.84.8

347.3

359.8

336.4

469.45.4474.521.8

472.014.0

468.25.9482.820.5

476.020

Reanal. ofpyrolysis data

(1) Reanal. ofpyrolysis data

(2) Correlation

(1) FT MS(2) Negative ion

cycle(3) Negative ion

spectroscopy

(1) FT MS(2) Negative ion

cycle(3) Negative ion

spectroscopy

1997RUC/GER

(1) 1997RUC/GER

(2) 2002KRO/TUM

(1) 2000REE/KAS(2) 2001LAR/SQU

(3) 2001ERV/RAM

(1) 2000REE/KAS(2) 2001LAR/SQU

(3) 2001ERV/RAM

H H

H

H

H

21

H12

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1-methyl-naphthalene

fHo(1-naphthylmethyl) =60.4 (252.7)X = H X = H

X = CN X = H

X = H X = Me

2-methyl-naphthalene

X = H Y = H

X = Me Y = H

X = SO2Ph Y = H

X = CN Y = H

X = H Y = 3-Me

X = H Y = 6-Me

1-ethylnaphthalene

4,5-methylene-phenathrene

Chapter Three:Tabulated BDEs of CH Bonds 39

(1) 84.31.5(2) 85.11.5(3) 87.3

(4) 81.3

(5) 86.8

(1) 85.6

(1) 87.1

(2) 89

(3) 81.4

(1) 86.8

(1) 87.3

87.1

81

352.76.3356.16.3365.1

340.2

363.3

358.3

364.6

372.4

340.6

363.1

365.2

364.4

338.9

(1) VLPP(2) Review(3) Correlation

(4) AOP

(5) Correlation

(1) Correlation

(2) AOP

(3) AOP

Correlation

AOP

(1) 1980MCM/TRE(2) 1982MCM/GOL(3) 2000DEN/DEN

(4) 1988BOR/CHE(b)

(5) 2002KRO/TUM

(1) 2002KRO/TUM

(2) 1988BOR/BAU

(3) 1988BOR/CHE(b)

2000DEN/DEN

1989BOR/HAR

(continued)

XCH

H

12

X

H

CH X123

4567

8

Y

CCH3

H

H

12

HH2C CH

45

03-1589.qxd 11-11-02 8:44 PM Page 39

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Table 3.4 (continued) CH BDEs in Aromatic Hydrocarbons

40 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe broken bonds

(boldface = recommended(boldface =

data; referencesdissociated atom)

in parentheses)Methods

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

9,10-dihydroanthracene,substituted

fHo(9,10-dihydroanthracen-9-yl) = 62.4 (261.1)X = H, X = H

X = H X = Ph

X = Me X = Me

9,10-dihydroanthracene,substituted

9,10-dihydroanthracene,substituted

(1) 78(2) 78(3) 77(4) 76.3(5) 83.0

(6) 79(5) 84.5

(7) 77(5) 81.5

84.9

83.3

326.4326.4322.2319.2347.3

330.5353.5

322.2341.0

355.2

348.5

(1) AOP(2) PAC(3) Kinetics(4) VLPP(5) Reanal. of

pyrolysis data

(6) AOP

(7) PAC

Reanal. ofpyrolysis data

Reanal. ofpyrolysis data

(1) 1988BOR/CHE(2) 1989GRI/SIM(3) 1990MAL/MCM(4) 1991STE/BRO(5) 1997RUC/GER

(6) 1991BOR/CHE

(7) 1989GRI/SIM

1997RUC/GER

1997RUC/GER

X

XH

H

H H

PhPh

H H Me

MeMe

Me

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Chapter Three:Tabulated BDEs of CH Bonds 41

xanthece, substituted

X = H

X = Me

X = CN

X = SO2Ph

X = Ph

X = p-MeC6H4

X = p-MeOC6H4

X = p-FC6H4

X = p-ClC6H4

X = p-CF3C6H4

9,10-dihydroacridine,substituted

X = NH

X = NCH3

thioxanthece

(1) 74(2) 75.5(3) 75.2(4) 80.7

(4) 77.6

(5) 69

(6) 82

(5) 76(3) 74.6(7) 76.7

(5) 75.6

(5) 74.3(7) 76.2

(5) 76.8(7) 76.4

(5) 73.9(7) 78.1

(5) 78.3(7) 78.1

80.0

80.0

74.6

309.6315.9314.6337.6

324.7

288.7

343.1

318.0312.1320.9

316.3

310.9318.8

321.3319.7

309.2326.8

327.6326.8

334.8

334.8

312.1

(1) VLPP(2) AOP(3) AOP(4) Reanal. of

pyrolysis data

(5) AOP

(6) AOP

(7) AOP

Reanal. ofpyrolysis data

AOP

(1) 1991STE/BRO(2) 1991BOR/CHE(3) 1997ARN/FLO(4) 1997RUC/GER

(5) 1992ZHA/BOR

(6) 1988BOR/CHE

(7) 1993ARN/FLO

1997RUC/GER

1997ARN/FLO

(continued)

X H

O

X

H H

H H

S

03-1589.qxd 11-11-02 8:44 PM Page 41

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Table 3.4 (continued) CH BDEs in Aromatic Hydrocarbons

42 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe broken bonds

(boldface = recommended(boldface =

data; referencesdissociated atom)

in parentheses)Methods

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

10-hydroanthracen-9-one

fluorene, substituted

fHo(9-fluorenyl) = 71.72.0(300.08.4)

Y = H

Y = 2-PhSO2

Y = 2-CN

Y = 2-NO2

Y = 2-MeO

Y = 2-Me2N

Y = 2-PhSO2

Y = 2,7-Br29-CO2Me

fluorene, substituted

-*X = 9-CN

80.2

(1) 80.1(2) 82.2(3) 81.22.4(4) 82.02

(5) 82.6

(6) 80

(6) 80

(6) 81

(7) 80

(6) 80

(8) 79.7

(6) 76.5

(1) 74.8

335.6

335.1343.9339.710.0343.18.4

345.6

334.7

334.7

338.9

334.7

334.7

333.5

320.1

313.0

Reanal. ofpyrolysis data

(1) VLPP(2) Electrochem.(3) ICR(4) Reanal. of

pyrolysis data(5) Reanal. of

pyrolysis data

(6) AOP

(7) AOP

(8) AOP

AOP

1997RUC/GER

(1) 1991STE/BRO(2) 1992PAR(3) 1997ROM/JAN(4) 1994RAK/VER

(5) 1997RUC/GER

(6) 1992ZHA/BOR

(7) 1994ZHA/BOR(b)

(8) 1993ZHA/BOR

(1) 1991BOR/ZHA

H H

O

H H

12

34567

8 9

Y

9

X H

03-1589.qxd 11-11-02 8:44 PM Page 42

Copyright 2003 by CRC Press LLC

Chapter Three:Tabulated BDEs of CH Bonds 43

X = 9-SO2Ph

X = 9-PhS

X = 9-Me2N

X = 9-(2,4,6-Me3C6H2)

X = 9-PhCH2(Me)N

X = 9-(iPr)2N

X =

X =

X =

X =

X =

X = 9-Ph

X = 9-C6F5

X = 9-mesityl

X = 9-MeOCO

X = 9-c-C4H8N

X = 9-c-C5H10N

X = 9-PhCH(Me)N

X = 9-CH(Me)(CH2)2C(Me)NH

X = 9-C(Me)2(CH2)2C(Me)2N

X = 9-MeX = fHo(R) = 64.12

(268.28.4)

(1) 81.9

(1) 74.6

(1) 71.5

(2) 74.5

(3) 72.5

(3) 73

(3) 76

(3) 68

(3) 72

(3) 72

(3) 71

(6) 74

(4) 78.2

(6) 74.5

(6) 76

(6) 68

(6) 72

(6) 72.5

(6) 72

(6) 71

(7) 75.4(8) 79.72(9) 78.5

342.7

312.1

299.2

311.7

303.3

305.4

318.0

284.5

301.2

301.2

297.1

309.6

327.2

311.7

318.0

284.5

301.2

303.3

301.2

297.1

315.5333.5328.4

(2) 1991BOR/ZHA

(3) 1992ZHA/BOR

(4) 1993ZHA/BOR

(5) 1994ZHA/BOR(b)

(6) 1994ZHA/BOR(c)

(7) 1994BOR/ZHA(8) 1998BRO/BEC(9) 2002KRO/TUM

(continued)

9-Me

Me

Me

N9

N9

N9

9 N

03-1589.qxd 11-11-02 8:44 PM Page 43

Copyright 2003 by CRC Press LLC

Table 3.4 (continued) CH BDEs in Aromatic Hydrocarbons

44 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe broken bonds

(boldface = recommended(boldface =

data; referencesdissociated atom)

in parentheses)Methods

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

X = 9-Et

X = 9-n-Pr

X = 9-iPr

X = 9-sBu

X = 9-tBu

X = 9-neoC5H11

X = 9-PhC(Me)2CH2

X = 9-PhCH2

X = 9-MeS

X = 9-EtS

X = 9-iPrS

X = 9-tBuS

X = 9-PhS

X = 9-MeSO2

X = 9-EtSO2

X = 9-iPrSO2

X = 9-PhSO2

X = 9-(p-BrPh)SO2

X = 9-MeO

X = 9-EtO

X = 9-iPrO

X = 9-tBuO

X = 9-PhO

X = 9-Me3SiCH2

X = 9-Me3N+, Cl

X = 9-PyN+, Br

(7) 76.2

(7) 76.1

(7) 77.3

(7) 75.1

(7) 79.9

(7) 73.6

(7) 73.8

(7) 75.9

(7) 74.6

(7) 74.3

(7) 74.3

(7) 74.8

(7) 74.8

(7) 82.1

(7) 81.4

(7) 81.1

(7) 79.7

(7) 82

(7) 73.0

(7) 72.9

(7) 72.7

(7) 74.0

(7) 74.3

(9) 76.3

(5) 84.6

(4) 80.9

318.8

318.4

323.4

314.2

334.3

307.9

308.8

317.6

312.1

310.9

310.9

313.0

313.0

343.5

340.6

339.3

333.5

343.1

305.4

305.0

304.2

309.6

310.9

319.2

354.0

338.5

(9) 1996ZHA/BOR

03-1589.qxd 11-11-02 8:44 PM Page 44

Copyright 2003 by CRC Press LLC

Chapter Three:Tabulated BDEs of CH Bonds 45

X = 9-Ph3P+, Br

X = 9-nBu3P+, Br

X = 9-Ph3As+, Br

X = 9-Me2S+, Br

X = 9-Me2Se+, Br

X = 9-tBu2Te+, Br

X = 9-Me3N+(2-PhSO2), Br

1,2,3,4,4a,9a-hexahydrofluorene

acenaphthene

3,4,5-trihydroacenaphthene

tetrahydroacenaphthene

(5) 81.6

(10) 83.0

(10) 82.6

(10) 77.6

(10) 78.7

(10) 77.3

(4) 85.7

79.3

83.7

78.8

75.8

341.4

347.3

345.6

324.7

329.3

323.4

358.6

332.0

350.0

329.7

317.0

Correlation

Correlation

Correlation

Correlation

(10) 2000CHE/LIU

2002KRO/TUM

2000DEN/DEN

1995STUM/DEN

2002KRO/TUM

(continued)

HH

HH

HH

HH

03-1589.qxd 11-11-02 8:44 PM Page 45

Copyright 2003 by CRC Press LLC

BDEsThe broken bonds

(boldface = recommended(boldface =

data; referencesdissociated atom)

in parentheses)Methods

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

9-anthracenylmethane,substituted

Y = H, X = HfHo(9-anthracenylmethyl) =80.7 (337.6)

X = CN

X = MeO

X = PhO

X = PhCO

X = NO2

X = PhS

X = PhSO2

Y = CN, X = MeO

Y = PhO

anthracene, substituted

Y = Cl

Y = Me

Table 3.4 (continued) CH BDEs in Aromatic Hydrocarbons

46 Handbook of Bond Dissociation Energies in Organic Compounds

(1) 81.0

(2) 81.8(3) 81.5(4) 84.10.5

(5) 78.7(6) 78.9

(5) 77.4(6) 77.5

(5) 78.6(6) 79.9

(6) 84.2

(6) 86.1

(6) 81.0

(6) 84.7

(5) 73.7

(5) 72.9

(1) 80.8

(1) 81.8(2) 78.1

338.9

342.3341.0351.92.1

329.3330.1

323.8324.3

328.7334.3

352.3

360.2

338.9

354.4

308.4

305.0

338.1

342.3326.7

(1) Analysisof exp.

(2) Review(3) AOP(4) Electrochem.

(5) AOP(6) AOP

(1) AOP

(2) Correlation

(1) 1980MCM/TRE

(2) 1982MCM/GOL(3) 1991BOR/CHE(4) 1991PAR/HAN

(5) 1991BAU/FAS(b)(6) 1993ZHA/BOR(b)

(1) 1993ZHA/BOR(b)

(2) 2002KRO/TUM

HCH

Y

X

H CH2

10

987

65 4

3

21

Y

03-1589.qxd 11-11-02 8:44 PM Page 46

Copyright 2003 by CRC Press LLC

Y = MeO

Y = Ph

Y = CHO

Y = PhCO

Y = CN

Y = NO2

Y = PhS

9-phenanthrenylmethane

fHo(9-phenanthrenylmethyl)= 74.4

(311.3)

9,10-dihydrophenanthrene

phenalene

benzanthrene

Chapter Three:Tabulated BDEs of CH Bonds 47

(1) 81.4

(1) 81.8

(1) 80.4

(1) 82.3

(1) 80

(1) 82.6

(1) 80.8

85.11.5

(1) 89.6

(2) 82.1(3) 81.6

(1) 643(2) 74.0

(1) 663(2) 76.0

340.6

342.3

336.4

344.3

334.7

345.6

338.1

356.16.5

374.9

343.7341.6

267.812.6309.6

276.112.6318.0

VLPP

(1) Reanal. ofpyrolysis data

(2) Correlation(3) Correlation

(1) AOP(2) Reanal. of

pyrolysis data

(1) AOP(2) Reanal. of

pyrolysis data

1982MCM/GOL

(1) 1997RUC/GER

(2) 2000DEN/DEN(3) 2002KRO/TUM

(1) 1990BAU/GOS(2) 1997RUC/GER

(1) 1990BAU/GOS(2) 1997RUC/GER

(continued)

H9

1012

34

56

7

8

CH2

H10 9

H

H

H

H

H

03-1589.qxd 11-11-02 8:44 PM Page 47

Copyright 2003 by CRC Press LLC

Table 3.4 (continued) CH BDEs in Aromatic Hydrocarbons

48 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe broken bonds

(boldface = recommended(boldface =

data; referencesdissociated atom)

in parentheses)Methods

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

triphenylene radical cation

1,2-benzofluorence

2,3-benzofluorence

methylbenzo(b)phenanthrene

6-methylchrysene

86.04.8

78.7

(1) 78.8(2) 78.4

88.6

85.7

359.920.0

329.3

329.7328.0

370.8

358.7

PIMS

AOP

(1) VLPP(2) AOP

Correlation

Correlation

1997LIN/LIF

1991BOR/CHE

(1) 1991STE/BRO(2) 1991BOR/CHE

2002KRO/TUM

2002KRO/TUM

H

H H

12

34567

89

98

76 5 4 3

21

HH

CH2H

CH2 H

03-1589.qxd 11-11-02 8:44 PM Page 48

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Chapter Three:Tabulated BDEs of CH Bonds 49

1,2-dihydropyrene

1,2,3,6-tetrahydropyrene

(E)-9,10-diphenyl-9,10-dihydroanthracene

(Z)-9,10-diphenyl-9,10-dihydroanthracene

dodecahedrane

81.6

81.6

81.5

79.4

923

341.4

341.4

341.0

332.2

384.912.6

Correlation

Correlation

Reanal. ofpyrolysis data

Reanal. ofpyrolysis data

FT-MS

2000DEN/DEN

2002KRO/TUM

1997RUC/GER

1997RUC/GER

2000BRO/KAS(a)

HH

HH

21

HH

H

H

H

H

H

03-1589.qxd 11-11-02 8:44 PM Page 49

Copyright 2003 by CRC Press LLC

Table 3.5 CH BDEs in Halogenated Hydrocarbons

50 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe broken bonds

(boldface = recommended(boldface =

data; referencesdissociated atom)

in parentheses)Methods

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

trifluoromethaneCF3HfHo(R) = 111.40.9

(466.13.8)

difluoromethaneCHF2HfHo(R) = 57.11

(238.94.2)

fluoromethaneCH2FHfHo(R) = 7.61

(31.84.2)

chlorodifluoromethaneCClF2HfHo(R) = 66.72

(279.18.4)

dichlorofluoromethaneCCl2FHfHo(R) = 21.32

(89.08.4)

chlorofluoromethaneCHClFHfHo(R) = 14.52.4

(60.710.0)

(1) 106.71(2) 107(3) 107.4(4) 106.31.3(5) 108.9

(1) 97.41.3(2) 1012(3) 103.2 1(4) 1012(5) 101.81.1

(1) 101.31(2) 1002

(1) 101.61(2) 100.72

(1) 98.91.2(2) 98.22(3) 97.7

(1) 100.82.4(2) 99.4

446.44.2447.7449.4444.85.4455.6

407.55.4422.68.4431.84.2422.68.4425.84.6

423.84.2418.48.4

425.1 4.2421.78.4

413.85.0410.98.4408.8

421.710.0415.9

(1) Photolysis(2) Review(3) Derived(4) Recommend.(5) SPST

(1) Kinetics(2) Elimination(3) Iodination(4) Kinetics(5) Review

(1) Iodination(2) Kinetics

(1) Review(2) Photobromin.

(1) Bromination(2) Photobromin.(3) Review

(1) Bromination(2) Review

(1) 1972BAS/WHI(2) 1982MCM/GOL(3) 1997ASH/RUS(4) 1998CHA(5) 1999TSA

(1) 1969PRI/PER(2) 1971KER/TIM(3) 1983PIC/ROD(4) 1983MAR/PAR(5) 2001LAZ/PRO

(1) 1983PIC/ROD(2) 1983MAR/PAR

(1) 1982MCM/GOL(2) 1992MIY/TSC

(1) 1987TSC/PAD(2) 1992MIY/TSC(3) 1997POU/PAU

(1) 1987TSC/PAD(2) 1997POU/PAU

3.5Halogenated hydrocarbons

03-1589.qxd 11-11-02 8:44 PM Page 50

Copyright 2003 by CRC Press LLC

Chapter Three:Tabulated BDEs of CH Bonds 51

trichloromethaneCCl3HfHo(R) = 17.00.6

(71.12.5)

dichloromethaneCHCl2HfHo(R) = 22.31.0

(93.34.2)

chloromethaneCH2ClHfHo(R) = 28.00.7

(117.22.9)

bromochloromethaneCHBrClHfHo(R) = 36.83

(154.013)

tribromomethaneCBr3HfHo(R) = 49.02

(205.08.4)

dibromomethaneCHBr2HfHo(R) = 45.02.2

(188.39.2)

(1) 95.81(2) 95.2(3) 94.92

(4) 93.80.6

(1) 99.02

(2) 98.41.2(3) 97.22

(4) 96.20.6

(5) 97.31.0

(1) 100.81(2) 99.42

(3) 100.10.6

(4) 1002(5) 99.9

93.991.3

(1) 96.01.6(2) 95.42

(1) 103.72

(2) 99.71.8(3) 97.92

(4) 98.2

400.84.2398.3397.18.4

392.52.5

414.28.4

411.75.0406.78.4

402.52.7

407.14.2

421.74.2415.98.4

419.02.3

418.48.4418

393382.0

401.76.7399.28.4

433.98.4

417.17.5409.68.4

411

(1) Bromination(2) Review(3) Electron

impact(4) PIMS

detection

(1) Toluenecarrier tech.

(2) Bromination(3) Electron

impact(4) PIMS

detection(5) Review

(1) Bromination(2) Electron

impact(3) PIMS

detection(4) Review(5) FT-ICR

FT-ICR

(1) Bromination(2) Electron

impact

(1) Toluenecarrier tech.

(2) Bromination(3) Electron

impact(4) Review

(1) 1973MEN/GOL(2) 1983WEI/BEN(3) 1988HOL/LOS

(4) 1991HUD/JON

(1) 1958PRI/TRO

(2) 1987TSC/PAD(3) 1988HOL/LOS

(4) 1996SEE

(5) 1997POU/PAU

(1) 1987TSC/PAD(2) 1988HOL/LOS

(3) 1996SEE

(4) 1997POU/PAU(5) 2000BOR/ING

2000BOR/ING

(1) 1971KIN/GOL(2) 1988HOL/LOS

(1) 1958PRI/TRO

(2) 1987TSC/PAD(3) 1988HOL/LOS

(4) 2000BOR/ING

(continued)

03-1589.qxd 11-11-02 8:44 PM Page 51

Copyright 2003 by CRC Press LLC

Table 3.5 (continued) CH BDEs in Halogenated Hydrocarbons

52 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe broken bonds

(boldface = recommended(boldface =

data; referencesdissociated atom)

in parentheses)Methods

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

bromomethaneCH2BrHfHo(R) = 40.41

(169.04.2)

diiodomethaneCHI2HfHo(R) = 79.82.2

(333.99.2)

iodomethaneCH2IHfHo(R) = 54.92

(229.78.4)

pentafluoroethaneCF3CF2HfHo(R) = 213.41

(892.94.2)

1,1,2,2-tetrafluoroethaneCHF2CF2HfHo(R) = 158.94.5

(664.818.8)

1,2,2-trifluoroethaneCH2FCF2HfHo(R) = 107.53.5

(449.814.6)

(1) 102.02

(2) 101.61(3) 100.82

1032

(1) 1032(2) 103.52

(3) 103.20.7

(1) 103.11.5(2) 102.70.5

103.04.5

103.53.5

426.88.4

425.14.2421.78.4

431.08.4

431.08.4433.08.4

431.62.8

431.46.3429.72.1

431.018.8

433.014.6

(1) Toluenecarrier tech.

(2) Bromination(3) Electron

impact

Review

(1) Review(2) Electron

impact(3) Kinetics

(1) Kinetics(2) Photolysis

Review

Review

(1) 1958PRI/TRO

(2) 1987TSC/PAD(3) 1988HOL/LOS

1970ONE/BEN

(1) 1970ONE/BEN(2) 1988HOL/LOS

(3) 2002SEE

(1) 1972BAS/WHI(2) 1981EVA/WHI

1996ZAR/WES

1996ZAR/WES

03-1589.qxd 11-11-02 8:44 PM Page 52

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Chapter Three:Tabulated BDEs of CH Bonds 53

1,2,2-trifluoroethaneCHF2CFHHfHo(R) = 1093.5

(456.114.6)

1,1,1-trifluoroethaneCF3CH2HfHo(R) = 123.62

(517.18.4)

1,1-difluoroethaneCH3CF2HfHo(R) = 72.32

(302.58.4)

1,2-difluoroethaneCH2FCHFHfHo(R) = 57.03

(238.512.6)

1,1-difluoroethaneCHF2CH2HfHo(R) = 68.33.5

(285.814.6)

fluoroethaneCH2FCH2HfHo(R) = 14.22

(59.48.4)

fluoroethaneCH3CHFHfHo(R) = 16.82

(70.38.4)

1-chloro-2,2,2-trifluoro-ethaneCF3CHClH

102.03.5

106.71.1

99.51

98.83

103.53.5

(1) 103.62(2) 100.82

(1) 97.32(2) 98.22

101.81.5

426.814.6

446.44.5

416.34.2

413.412.6

433.014.6

433.58.4421.78.4

407.18.4410.98.4

425.96.3

Review

Kinetics

Iodination

UV-flashphotolysis

Review

(1) Review(2) Photobromin.

(1) Bromination(2) Photobromin.

Review

1996ZAR/WES

1974WU/ROD

1977PIC/ROD

1983MAR/PAR

1996ZAR/WES

(1) 1996ZAR/WES(2) 1996MIY/OZA

(1) 1987TSC/SAL(b)(2) 1996MIY/OZA

1982MCM/GOL

(continued)

03-1589.qxd 11-11-02 8:44 PM Page 53

Copyright 2003 by CRC Press LLC

Table 3.5 (continued) CH BDEs in Halogenated Hydrocarbons

54 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe broken bonds

(boldface = recommended(boldface =

data; referencesdissociated atom)

in parentheses)Methods

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

1-bromo-1-chloro-2,2,2-trifluoroethaneCF3CClBrHfHo(R) = 120.52

(504.28.4)

2-chloro-1,2,2-trifluoro-ethaneCClF2CHFHfHo(R) = 107.73

(450.612.6)

pentachloroethaneCCl3CCl2HfHo(R) = 8.41.3

(35.15.4)

1,1,2,2-tetrachloroethaneCHCl2CCl2HfHo(R) = 5.62

(23.48.4)

1,1-dichloroethaneCH3CCl2HfHo(R) = 10.20.4

(42.71.7)

chloroethaneCH3CHClHfHo(R) = 18.30.4

(76.61.5)

96.61.5

98.50.5

(1) 95.8(2) 952

942

(1) 93.40.4

(2) 95.11.2

(1) 95.7(2) 98.22

(3) 96.51(4) 97.20.4

404.26.3

412.12.1

400.8397.58.4

393.38.4

390.61.5

397.95.0

400.4410.98.4

403.84.2406.61.5

Review

Pyrolysis

(1) Photochlorin.(2) Shock tube

Shock tube

(1) PIMSdetection

(2) Kinetics

(1) Bromination(2) Electron

impact(3) Photobromin.(4) PIMD

detection

1982MCM/GOL

1998SKO/DYM

(1) 1969FRA/HUY(2) 1976LEW

1976LEW

(1) 1996SEE

(2) 1999MIY/TSC

(1) 1987TSC/SAL(b)(2) 1988HOL/LOS

(3) 1990MIY/TSC(4) 1996SEE

03-1589.qxd 11-11-02 8:44 PM Page 54

Copyright 2003 by CRC Press LLC

Chapter Three:Tabulated BDEs of CH Bonds 55

chloroethaneCH2ClCH2HfHo(R) = 22.20.6

(93.02.4)

1,1-dibromoethaneCH3CBr2HfHo(R) = 33.51.3

(140.25.4)

bromoethaneCH2BrCH2HfHo(R) = 32.3

(135.1)

bromoethaneCH3CHBrHfHo(R) = 30.3

(126.8)

trifluoroethyleneCF2=CFH

1,1-difluoroethyleneCF2=CHHfHo(R) = 22.22

(92.98.4)

(Z)-1,2-difluoroethyleneCHF=CFHfHo(R) = 12.12

(50.68.4)

1,1-difluoro-2-chloroethyleneCF2=CClH

(1) 101.72

(2) 100.71(3) 101.10.6

94.91.2

99.22

(1) 96.4(2) 94.22

(3) 97.21

111.02.0

1102

1102

1092

425.58.4

421.34.2423.12.4

397.15.0

415.18.4

403.3394.18.6

406.74.2

464.48.4

460.28.4

460.28.4

456.18.4

(1) Electronimpact

(2) Photobromin.(3) PIMS

detection

Kinetics

Electron impact

(1) Bromination(2) Electron

impact(3) Photobromin.

Correlation

Correlation

Correlation

Correlation

(1) 1988HOL/LOS

(2) 1990MIY/TSC(3) 1998SEE

1999MIY/TSC

1988HOL/LOS

(1) 1987TSC/SAL(b)(2) 1988HOL/LOS

(3) 1990MIY/TSC

1981STE/ROW

1981STE/ROW

1981STE/ROW

1981STE/ROW

(continued)

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Copyright 2003 by CRC Press LLC

Table 3.5 (continued) CH BDEs in Halogenated Hydrocarbons

56 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe broken bonds

(boldface = recommended(boldface =

data; referencesdissociated atom)

in parentheses)Methods

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

(E)-1,2-chloro-2-fluoro-ethyleneCFCl=ClH

(Z)-1,2-dichloroethyleneCHCl = CClHfHo(R) = 56.12

(234.78.4)

chloroethyleneCH2 = CClHfHo(R) > 60.4

(>252.7)

1,1,1,2,2,3,3-heptafluoro-propaneCF3CF2CF2H

1,1,1,2,3,3,3-heptafluoro-propaneCF3CFHCF3

1-chloropropaneCH3CH2CHClHfHo(R) = 13.50.8

(56.63.3)

1-chloropropaneCH2ClCH2CH3

1-fluoropropeneCH2 = CH-CHFH

1082

1072

>103.6

(1) 1042(2) 103.3

103.50.6

97.30.8

97.80.9

88.61.1

451.98.4

447.78.4

>433.5

435.18.4432.2

433.02.5

407.03.5

409.33.9

370.74.6

Correlation

Correlation

PIMS detection

(1) Review(2) Bromination

Kinetics

Derived

Derived

VLPP

1981STE/ROW

1981STE/ROW

1989RUS/SEN

(1) 1982MCM/GOL(2) 1983EVA/WEE

1983EVA/WEE

1998SEE

1998SEE

1973ALF/GOL

03-1589.qxd 11-11-02 8:44 PM Page 56

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Chapter Three:Tabulated BDEs of CH Bonds 57

1-chloropropeneCH2 = CH-CHClH

1-bromopropeneCH2 = CH-CHBrHfHo(R) = 48.11.1

(201.34.6)

pentafluorobenzeneC6F5HfHo(R) = 130.92

(547.78.4)

9-pentafluorophenyl fluorine9-C6F5FlH

tri(2,3,5,6-tetrafluoro-phenyl)phenyl methane(pHC6F4)3CH

88.61.1

89.41.1

113.9

78.2

82.3

370.74.6

374.04.6

476.6

327.2

344.3

VLPP

VLPP

Toluene carriertech.

AOP

AOP

1973ALF/GOL

1973ALF/GOL

1974KRE/PRI

1993BOR/ZHA(b)

1993BOR/ZHA(b)

(continued)

3.6Organic compounds containing heteroatoms3.6.1CH BDEs with -OH, -OR, -C(O), and -C(O)O

Table 3.6.1 CH BDEs with -OH, -OR, -C(O), and -C(O)O

BDEsThe 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

methanolHCH2OHfHo(R) = 4.080.8

(17.073.35)

ethanolCH3CH2OH

(1) 95.91.5(2) 96.0(3) 96.20.2(4) 96.060.15(5) 96.20.3

(1) 931.0(2) 94.6

401.26.3401.7402.50.8401.920.63402.51.3

389.14.2395.8

(1) Iodination(2) SPST(3) PIMS detect.(4) Recommend.(5) Resonance

fluorescence

(1) Iodination(2) SPST

(1) 1973ONE/BEN(2) 1981TSA(3) 1993RUS/BER(4) 1994BER/ELL(5) 1996DOB/BER

(1) 1973ALF/GOL(2) 1981TSA

03-1589.qxd 11-11-02 8:44 PM Page 57

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Table 3.6.1 (continued) CH BDEs with -OH, -OR, -C(O), and -C(O)O

58 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe 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

fHo(R) = 13.30.8(55.63.5)

ethanolCH3CH2OHfHo(R) = 7.0

(29.3)

propanolCH3CH2CH2OHfHo(R) = 19.41

(818)

propanolCH3CH2CH2OHfHo(R) = 18.82

(78.78.4)

propanolCH3CH2CH2OHfHo(R) = 16.02

(66.98.4)

propan-2-ol(CH3)2CHOHfHo(R) = 26.31

(110.04.2)

propan-2-ol(CH3)2CHOHfHo(R) = 23.01

(96.24.2)

(3) 94.8

(4) 982(5) 95.91

101.3

(1) 93.7(2) 93.2

94.32

97.12

(1) 911(2) 89.31.7(3) 91.72(4) 93.0

94.32

396.6

410.08.4401.24.2

423.8

392.0389.9

394.68.4

406.38.4

380.74.2373.67.1383.78.4389.1

394.68.4

(3) Electronimpact

(4) PIMS detect.(5) Review

MS

(1) SPST(2) Correlation

AE

AE

(1) Review(2) PAC(3) AE(4) Correlation

AE

(3) 1991HOL/LOS

(4) 1994RUS/BER(5) 1999ATK/BAU

1990TAK

(1) 1999TSA(2) 2000DEN/DEN

1992HOL

1992HOL

(1) 1982MCM/GOL(2) 1989KAM/GRI(3) 1992HOL(4) 2000DEN/DEN

1992HOL

03-1589.qxd 11-11-02 8:44 PM Page 58

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Chapter Three:Tabulated BDEs of CH Bonds 59

allyl alcoholCH2=CHCH2OHfHo(R) = 02

(08.4)

2-methylpropan-2-ol(CH3)3COHfHo(R) = 26.82

(112.18.4)

penta-1,4-dien-3-ol(CH2=CH)2CHOHfHo(R) = 22.12

(92.58.4)

cyclohexanol

benzyl alcoholC6H5CH2OH

1-phenylethanolPhMeC(OH)H

diphenylmethn-1-olPh2CHOHfHo(R) = 36.41.5

(152.36.3)

ethane-1,2-diol(CH2OH)2fHo(R) = 52.62

(220.18.4)

(1) 81.61.8(2) 80.1(3) 85.2

(1) 100.02.0(2) 99.1(3) 100.0

89

92.4

87.5

88.3

75.41.5

(1) 89.62.2(2) 92.1(3) 95.6

341.47.5355.1356.5

418.48.4414.6418.6

372.4

386.7

366.3

369.4

315.56.3

374.99.2385.3400.0

(1) Iodination(2) PAC(3) Correlation

(1) Review(2) APC(3) Correlation

PAC

Correlation

Correlation

Correlation

PAC

(1) PAC(2) AE(3) Correlation

(1) 1973ALF/GOL(2) 1992ARN/CAL(3) 2000DEN/DEN

(1) 1982MCM/GOL(2) 1989KAM/GRI(3) 2000DEN/DEN

1991CLA/CUL

2000DEN/DEN

2000DEN/DEN

2000DEN/DEN

1992ARN/CAL

(1) 1989KAM/GRI(2) 1992HOL(3) 2000DEN/DEN

(continued)

OH

H

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Table 3.6.1 (continued) CH BDEs with -OH, -OR, -C(O), and -C(O)O

60 Handbook of Bond Dissociation Energies in Organic Compounds

BDEsThe 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

1,4-butanediolHOCH2(CH2)2(OH)CHH

dimethyl etherCH3OCH3fHo(R) = 01

(04.2)

difluoromethyltrifluoromethyl etherCHF2OCF3

bis(difluoromethyl) etherCHF2OCHF2

methyl trifluoromethyl etherCH3OCF3

ethyl methyl etherCH3OCH2CH3fHo(R) = 10.82

(45.28.4)

diethyl etherCH3CH2OCH2CH3fHo(R) = 19.41

(81.24.2)

diisopropyl ether(CH3)2CHOCH(CH3)2

95.4

(1) 95.5(2) 931(3) 96.1(4) 95.3

1061

1041

1021

93.0

(1) 91.70.4(2) 93(3) 94.8

(1) 93.9

(2) 90.4

399.2

399.6389.1402.1398.7

443.54.2

435.14.2

426.84.2

389.1

383.71.7389.1396.5

392.9

378.2

Correlation

(1) Photodissocn.(2) Review(3) Review(4) Correlation

Kinetics

Kinetics

Kinetics

AE

(1) VLPP(2) PAC(3) Correlation

(1) Reanal. ofpyrolysis data

(2) Correlation

2000DEN/DEN

(1) 1967LOU/LAI(2) 1969GOL/BEN(3) 1999ATK/BAU(4) 2000DEN/DEN

1995HSU/DEM

1995HSU/DEM

1995HSU/DEM

1991HOL/LOS

(1) 1984KON/BEN(2) 1986BUR/MAJ(3) 2000DEN/DEN

(1) 1998BRO/BEC

(2) 2000DEN/DEN

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Chapter Three:Tabulated BDEs of CH Bonds 61

ethyl tert-butyl etherCH3CH2OtC(CH3)3

dibenzyl etherPhCH2OCH2Ph

cyclohexyl methyl ethercyclo-C6H11OMe

dimethoxymethane(MeO)2CH2

1,1-dimethoxyethane(MeO)2CmeH

Oxirane

fHo(R) = 35.81.5 (149.86.3)

tetrahydrofuran

fHo(R) = 4.31.5 (18.06.3)

formaldehydeHCOHfHo(R) = 9.960.20

(41.670.84)

96.9

84.8

89.9

92.9

88.2

100.51.5

(1) 921(2) 92.11.6(3) 92

(1) 87.01