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431

Alkoxy radicals in the gaseous phase: ␤-scission

reactions and formation by radical addition to
carbonyl compounds
Arvi Rauk, Russell J. Boyd, Susan L. Boyd, David J. Henry, and Leo Radom

Abstract: The structures and reactivities of the alkoxy radicals methoxy (CH3O·), ethoxy (CH3CH2O·), 1-propoxy
(CH3CH2CH2O·), 2-propoxy ((CH3)2CHO·), 2-butoxy (CH3CH2CH(CH3)O·), tert-butoxy ((CH3)3CO·), prop-2-enoxy
(CH2=CHCH2O·), and but-3-en-2-oxy (CH2=CHCH(CH3)O·) have been investigated at the B3-LYP/6-31G(d) and CBS-
o ) were calculated with CBS-RAD for all the alkoxy radicals, the
RAD levels of theory. Enthalpies of formation (∆ f H298
carbonyl and radical products of β-scission reactions, and the transition structures leading to them. The mean absolute
o values is 5.4 kJ mol–1. Eyring (∆H ‡, ∆H ‡ , ∆G ‡ )
deviation between the predicted and available experimental ∆ f H298 0 298 298
and Arrhenius (log A, Ea) activation parameters for both the forward (β-scission) and reverse (radical addition to car-
bonyl) pathways were calculated. Agreement with available experimental data is very good, generally within 1–5 kJ
mol–1 for Ea, and 0.5 for log A. The transition structures are found to be substantially polarized, with the departing
radical slightly positive, the O atom negative, and the rest of the molecule positive. The barriers for the β-scission reac-
tions decrease with decreasing endothermicity and with decreasing ionization energy of the departing radical.

Key words: alkoxy, alkoxyl, radical, addition, carbonyl, β-scission, calculaton, electronic structure, B3LYP, CBS-RAD,
thermochemistry.

Résumé : Faisant appel à des calculs théoriques aux niveaux B3-LYP/6-31G(d) et CBS-RAD de la théorie, on a étudié
les structures et les réactivités des radicaux alkoxy, méthoxy (CH3O·), éthoxy (CH3CH2O·), 1-propoxy (CH3CH2CH2O·),
2-propoxy [(CH3)2CHO·], 2-butoxy [CH3CH2CH(CH3)O·], tert-butoxy [(CH3)3CO·], prop-2-énoxy (CH2=CHCH2O·) et
but-3-én-2-oxy [CH2=CHCH(CH3)O·]. On a calculé les enthalpies de formation, ∆ f H298 o , au niveau CBS-RAD de la
théorie pour tous les radicaux alkoxy, tous les produits carbonylés et tous les produits radicalaires provenant de réac-
tions de β-scission et toutes les structures de transition qui y conduisent. La déviation absolue moyenne entre les
o expérimentales disponibles est de 5,4 kJ mol–1. On a aussi calculé les paramètres
valeurs prédites et les valeurs de ∆ f H298
d’activation d’Eyring (∆H0 , ∆H298 , ∆G298
‡ ‡ ‡
) et d’Arrhenius (log A, Ea) pour la réaction vers la droite (β-scission) et pour
la réaction inverse (addition d’un radical sur le carbonyle). L’accord entre les valeurs calculées et les valeurs expéri-
mentales disponibles est bon, généralement entre 1 et 5 kJ mol–1 pour les valeurs de Ea et de 0,5 pour le log A. On a
trouvé que les structures de transition sont assez polarisées alors que le radical qui se détache est légèrement positif,
l’atome d’oxygène est négatif et que le reste de la molécule est positif. Les barrières aux réactions de β-scission dimi-
nuent avec une augmentation du caractère endothermique et avec une diminution de l’énergie d’ionisation du radical
qui se détache.

Mots clés : alkoxy, alkoxyle, radical, addition, carbonyle, scission-β, calculs théoriques, structure électronique, B3LYP,
CBS-RAD, thermochimie.

[Traduit par la Rédaction] Rauk et al. 442

Received 24 October 2002. Published on the NRC Research Press Web site at http://canjchem.nrc.ca on 9 April 2003.
Dedicated to Professor Don Arnold for his contributions to chemistry.
A. Rauk.1 Department of Chemistry, University of Calgary, Calgary, AB T2N 1N4, Canada.
R.J. Boyd. Department of Chemistry, Dalhousie University, Halifax, NS B3H 4J3, Canada.
S.L. Boyd. Department of Chemistry, Mount St. Vincent University, Halifax, NS B3M 2J6, Canada.
D.J. Henry and L. Radom. Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia.
1
Corresponding author (e-mail: rauk@ucalgary.ca).

Can. J. Chem. 81: 431–442 (2003) doi: 10.1139/V02-206 © 2003 NRC Canada

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432
Introduction
Alkoxy radicals (R1R2R3C–O·) are important intermediate
species in the combustion of hydrocarbons (1, 2), and in at-
mospheric chemistry (3–5). They can react by intramolecular
hydrogen abstraction, or by intermolecular hydrogen abstrac-
tion from a suitable donor (R′–H) to yield the corresponding
alcohol:
[1] R1R2R3C-O· + R′-H → R1R2R3C-OH + R′·
Alternatively, alkoxy radicals can undergo β-cleavage to
yield an alkyl radical plus a ketone or aldehyde in up to
three ways:
[2a] R1R2R3C-O· → R1· + R2R3C=O
[2b] → R2· + R1R3C=O
[2c] → R3· + R1R2C=O
In proteins, production of such radicals by oxidative pro-
cesses may lead to protein backbone cleavage (6). In gen-
eral, the pathway that leads to the most stable radical is
found to dominate the endothermic cleavage (7, 8) but ex-
ceptions have been noted in polycyclic systems (9) and have
been investigated computationally (10).
The reverse reaction, alkyl radical addition to the carbonyl
double bond:
[3] R1· + R2R3C=O → R1R2R3C-O·
is hindered by an activation energy (Ea(3)) which has empiri-
cally been found to depend on the ionization energy of the
radical (IE(R1·)) and the exothermicity of the reaction
(∆H(3)) (11):
[4] Ea(3) = 8.8[IE(R1·)] – 0.58|∆H(3)| – 26
where the ionization energy is in units of eV and the
enthalpy of the reaction is in kJ mol–1. The relationship with
the ionization energy was attributed (11) to a tight transition
structure with substantial polarization in the sense:
Additional evidence for charge separation in the TS may
be deduced from the observation of a large solvent effect for
the β-scission of tert-butoxy radical (12). In a similar man-
ner, barriers for the addition of alkyl and related radicals to
alkenes have also been found to be dependent on the reac-
tion enthalpy and the ionization energy of the radical but a
multiplicative-type relationship is found to better describe
this dependence (13).
We investigate here the factors affecting both the decom-
position and radical-addition pathways for a systematic se-
ries of saturated and unsaturated alkoxy radicals, by using
high-level quantum mechanical methods. A number of
alkoxy radicals, including some of the systems of interest
here, have been previously studied both experimentally, by
means of laser flash photolysis – laser-induced fluorescence,
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Can. J. Chem. Vol. 81, 2003
and computationally, by means of ab initio calculations, by
Viskolcz and co-workers (14–18), and others (19, 20). Their
work is discussed in the present context below.
Theoretical methods
Quantum mechanical calculations
Conventional ab initio (21) and density functional theory
(22) calculations were carried out with the Gaussian 94
(23a), Gaussian 98 (23b), and Molpro 2000 (24) suites of
electronic structure codes. Geometries and harmonic vibra-
tional frequencies were obtained for all species at the B3-
LYP/6-31G(d) level of theory. The vibrational frequencies
were used, after appropriate scaling (25), in the calculation
of thermodynamic and kinetic parameters including zero-
point vibrational energies (ZPVEs), and to characterize each
stationary point as a local minimum (no imaginary frequen-
cies), or as a transition structure (one imaginary frequency).
Higher-level energies were determined for all structures by
the CBS-RAD procedure, which has been developed to pro-
vide accurate thermochemistry for radical species (26). The
CBS-RAD(B3-LYP) combination employed here has been
found to yield good reaction enthalpies and barriers for the
addition of C-centered radicals to alkenes (13, 27).
Thermochemical procedures
Gas-phase thermodynamic functions, including thermal
enthalpy contributions (H° – H0o ) (where H° refers to
298.15 K) and entropies (S) may be accurately calculated
by application of standard statistical procedures (28).
Values derived experimentally are available in standard
sources (29–32).
Theoretical enthalpies of formation at 298.15 K for spe-
cies CaHbO may be calculated from the energies of the at-
omization reactions:
[5] aC + bH + O → CaHbO
by eqs. [6]–[8]:
[6] o (C H O) = ∆H + a∆ H o (C)
∆ f H298 a b (5) f 298
o (H) + ∆ H o (O)
+ b∆ f H298 f 298
where
[7] ∆H(5)(298.15 K) = ∆H(5)(0 K)
+ (H° – H0o )(CaHbO) – a(H° – H0o )(C)
– b(H° – H0o )(H) – (H° – H0o )(O)
and
[8] ∆H(5)(0 K) = ECBS(CaHbO) – aECBS(C)
– bECBS(H) – ECBS(O)
o ) and
In this procedure, the enthalpies of formation (∆ f H298
o
the (H° – H0 ) values for the gaseous atoms in their lowest
electronic states are taken from experiment (29) (kJ mol–1): C
(716.7, 6.535), H (218.0, 6.197), O (249.2, 6.724). The
CBS-RAD energies (ECBS(CaHbO)) for all species discussed
here are listed in Table 1. For the gaseous atoms in their
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Rauk et al. 433

o – H o (kJ mol–1), S (J K–1 mol–1), 298.15 K), and

Table 1. CBS-RAD energies (0 K, hartrees), thermodynamic functions (H298 0
enthalpies of formation (∆ f H o (kJ mol–1), 298.15 and 0 K).
S(g) o c
∆ f H298 ∆ f H0o
Species CBS-RADa nb o – Ho
H298 Exptl. Calcd. Exptl. Calcd. Calcd.
0
–0.49982 6.2 d
H· 1 114.7 114.6 218.0
CH3· –39.74402 1 10.6 194.2d 195.4 146.4 150.0 153.1
CH3CH2· –78.96993 1 12.9 252.0d 255.7 120.9 127.8 138.2
CH2=CH· –77.74177 1 10.6 233.6 300.0 301.9 306.1
CH3O· –114.87243 1 10.4 234.0e,f 17.2, 21g 21.0 28.7
CH3OH –115.53807 1 11.1 239.7d 237.7 –201.0 –201.8 –190.6
CH2=O –114.34253 1 10.0 218.8d 218.6 –108.6 –112.2 –108.3
H···CH2O·TS –114.83531 1 11.5 243.9 119.6 126.2
CH3CH2O· –154.10201 1 13.5 278.9e –15.5, –12g –9.9 4.2
h
CH3CH=O –153.58023 1 12.7 264.2 262.3 –166.2 –164.8 –154.2
H···CH(CH3)O·TS –154.06979 2 14.0 282.0 75.2 88.8
CH3···CH2O· TS –154.07668 1 14.9 285.9 58.0 70.7
CH3CH2CH2O· –193.32697 3 16.1 316.3e –41.4 –29.3 –8.2
CH3CH2CH=O –192.80566 3 15.6 304.7h 301.5 –185.6 –185.2 –167.8
H···CH(CH2CH3)O·TS –193.29559 3 17.1 316.4 54.1 74.2
CH3CH2···CH2O·TS –193.30643 3 17.8 326.6 26.4 45.8
(CH3)2CHO· –193.33181 1 16.1 305.4e –52.3, –46g –41.9 –20.9
(CH3)2C=O –192.81740 1 15.7i 294.9 h
299.5 –217.1 –215.9 –198.6
H···C(CH3)2O· TS –193.30390 1 17.0 304.9 32.2 52.4
CH3···CH(CH3)O·TS –193.31051 2 17.8 319.7 15.7 35.0
CH3CH2CH(CH3)O· –232.55793 6 19.6 351.4e –69.5 –63.4 –36.4
CH3CH2C(CH3)=O –232.04323 1 19.8 338.1h 337.1 –238.5 –235.9 –213.3
H···C(CH3)(CH2CH3)O·TS –232.53034 6 20.3 350.5 9.7 36.1
CH3···CH(CH2CH3)O·TS –232.53579 2 21.2 351.8 –3.6 21.8
CH3CH2···CH(CH3)O·TS –232.54080 6 21.1 360.7 –16.9 8.6
(CH3)3CO· –232.56511 1 19.6 322.6e,f –90.8, –83g –82.2 –55.2
CH3···C(CH3)2=O·TS –232.54493 1 21.1 338.3 –27.8 –2.2
CH2=CHCH2O· –192.11518 2 14.7 303.8e 102.8 116.7
CH2=CHCH=Oj –191.59751 1 13.9 278.0 –77.0k –62.9 –52.4
H···CH(CH=CH2)O·TS –192.08709 2 15.6 300.2 177.5 190.5
CH2=CH···CH2O·TS –192.08108l 3 17.6 328.7 195.2 206.3
CH2=CHCH(CH3)O· –231.34649 6 18.2 342.8e 67.6 87.7
CH2=CHC(CH3)=O –230.83280 1 17.7 313.4 –138.0k –108.2 –92.0
H···C(CH3)(CH=CH2)O·TS –231.32022 6 18.9 338.3 137.3 156.6
CH3···CH(CH=CH2)O·TS –231.32863l 6 19.5 346.6 115.9 134.6
CH2=CH···CH(CH3)O·TS –231.31577l 6 20.6 362.1 150.7 168.3
a
Energies for transition structures correspond to CBS-RAD–Scanmax values (see Table 2 and text) unless otherwise noted.
b
Number of significantly populated conformations (used to calculate entropies of mixing).
c
From ref. 32 unless otherwise noted.
d
Reference 29.
e
First excited state assumed to be significantly populated (adds R ln 2).
f
Rotational symmetry number = 3 assumed.
g o values from ref. 36.
∆ f H 300
h
Reference 34.
i
One methyl group rotation treated as a free rotation (contributes RT/2).
j
Energies refer to s-trans conformation.
k
Reference 30.
l
Standard CBS-RAD value.

lowest electronic states, the CBS-RAD energies are ECBS for convenience in Table 1 the enthalpies of formation for
(hartrees): C (–37.785143), H (–0.499818), O (–74.987034). the transition structures, even though the ∆fH would be a
Calculated enthalpies of formation are compared with somewhat artificial quantity for such species. In cases where
available experimental values in Table 1. We have included a substance exists as an equilibrium mixture of two or more

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434
conformers, the enthalpy of formation listed in Table 1 cor-
responds to that of the most stable conformer.
The entropy of a pure substance in the gas phase may be
expressed as a weighted sum of the entropies of individual
conformers, plus an entropy of mixing term (eq. [9]):
[9] Stotal = ΣixiSi – RΣixi ln xi ≅ S1 + R ln n
where xi is the mol fraction of conformer i, S1 is the entropy
of the most stable conformation, and n denotes the number
of significantly populated conformations (33).
The alkoxy radicals investigated in this study exhibit
Jahn–Teller distortions. We have accounted for the near de-
generacy of the A′ and A′ ′ states (Cs symmetry) by the addi-
tion of R ln 2 to the electronic entropy. In addition, for the
methoxy and tert-butoxy radicals we have adopted a rota-
tional symmetry number of 3. Calculated entropies are in-
cluded in Table 1, together with experimental values where
available.
Rates of reaction
In the thermodynamic formulation of transition-state the-
ory (TST) (34), the rate constant (kT) for a reaction at tem-
perature T is related to the free energy barrier (∆G‡) by
eq. [10] (35):
[10] kT = (kBT/h)(c°)1 – m exp(–∆G‡/RT)
where kB and h are Boltzmann’s and Planck’s constants, re-
spectively, R is the ideal gas constant, c° is the standard unit
of concentration (mol L–1), and m is the order of the reac-
tion. The factor ((c°)1 – m) provides the correct units for the
rate constant of unimolecular (m = 1) and bimolecular (m =
2) reactions. In the gas-phase standard state (T = 298.15 K)
the pressure is 1 atm and c° = 0.0408 mol L–1. We apply
eq. [10] for the calculation of both the (forward)
unimolecular β-scission reaction (eq. [2]) and the (reverse)
bimolecular radical-addition reaction (eq. [3]).
In Arrhenius rate theory, the rate constant is given by:
[11] kT = A exp(–Ea/RT)
The Arrhenius activation energy (Ea) is given by:
[12] Ea = ∆H‡ + mRT
The Arrhenius frequency factor (A) contains the entropy
of activation (∆S‡):
[13] A = (kBT/h)(c°)1 – mem exp(∆S‡/R)
Enthalpy barriers (∆H‡ (generally referred to in the course
of this paper simply as barriers)) are calculated directly from
enthalpies of formation of the appropriate species (or equiva-
lently from the calculated total energies and, if appropriate,
the enthalpy temperature corrections). In the present study, we
have not considered quantum mechanical tunneling. This
could in principle be important in the reactions involving hy-
drogen-atom scission and (or) addition but preliminary calcu-
lations suggest that the effect is not particularly significant.
Results and discussion
The energies of all species considered here are given in
Table 1. The variation with the theoretical level of selected
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Can. J. Chem. Vol. 81, 2003
properties of the transition structures are presented in Ta-
ble 2. Table 3 gives the kinetic parameters (∆H‡, ∆G‡, log A,
and Ea) and the reaction enthalpies (∆H) for β-scission reac-
tions (eq. [2]), while corresponding data for the reverse reac-
tion, radical addition to carbonyl (eq. [3]), are collected in
Table 4.
Enthalpies of formation
Enthalpies of formation, calculated from atomization ener-
gies as described above, are listed in Table 1. Comparison with
experimental values may be made for 17 species. The largest
discrepancy occurs for but-3-en-2-one (CH2=CHC(CH3)=O) for
o = –108.2 kJ mol–1) is
which the calculated value (∆ f H298
–1
29.8 kJ mol less negative than the experimental (∆ f H298 o =
–1
–138.0 kJ mol ). For the remaining 16 species, the mean
absolute deviation is 3.8 kJ mol–1, consistent with the accu-
racy expected from CBS-RAD (26). The second-largest dis-
crepancy (+14.1 kJ mol–1) also occurs for an α,β-unsaturated
carbonyl compound, acrolein ((E)-CH2=CHCH=O). The cal-
culated values for the heat of formation of the methoxy,
ethoxy, 2-propoxy, and tert-butoxy radicals are in close
agreement with the recent experimental results of Ramond et
al. (36), and support these values over the older results (32)
(which are generally less positive or more negative). Larger-
than-average differences between theory and experiment oc-
cur for two alkoxy radicals 1-propoxy (CH3CH2CH2O·,
+12.1 kJ mol–1) and 2-butoxy (CH3CH2CH(CH3)O·, +6.1 kJ
mol–1), and for the ethyl radical (CH3CH2·, +6.9 kJ mol–1).
Experimental reexamination may be warranted in these in-
stances. We are not aware of any experimental enthalpies of
formation for the prop-2-en-1-oxy (CH2=CHCH2O·) or but-
3-en-2-oxy (CH2=CHCH(CH3)O·) radicals.
Sensitivity of calculated barriers to TS geometry and
theoretical level
The barriers for the β-scission (forward, eq. [2]) and radi-
cal addition (reverse, eq. [3]) reactions are crucial for deter-
mining the kinetic fate of alkoxy radicals in atmospheric
chemistry and for understanding the combustion of hydro-
carbons. Columns 4 and 5 of Table 2 compare the B3-
LYP/6-31G(d) and CBS-RAD barriers (∆H0‡ ) for β-scission
of a number of the alkoxy radicals, in both cases using ge-
ometries and ZPVEs obtained at the B3-LYP/6-31G(d) level.
It is evident that the B3-LYP values are significantly higher
than the CBS-RAD values, by 13–20 kJ mol–1 for C-H
scission, and by 3–14 kJ mol–1 for C-C scission. By either
method, methyl-radical loss or ethyl-radical loss has a sig-
nificantly lower barrier than H-atom loss in species where
both channels are available.
The CBS-RAD procedure is expected to produce reason-
ably reliable estimates of the barriers provided that the ge-
ometries of the species derived at the B3-LYP/6-31G(d)
level are adequate. The results should be most sensitive to
the geometries of the transition structures. We have exam-
ined the appropriateness of the B3-LYP/6-31G(d) methodol-
ogy for determining the transition structures by calculating
the CBS-RAD energy at points along the bond-breaking co-
ordinate for most of the β-scission reactions. The breaking
C···H or C···C bond is stepped in 0.02 Å increments from the
B3-LYP/6-31G(d) transition structure with reoptimization of
all the remaining geometric parameters. The zero-point vi-
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Rauk et al. 435

Table 2. Dependence of transition structure bond length (r, Å) and reaction barrier (∆H0‡, kJ mol–1) on theoretical level.
B3-LYP/6-31G(d) CBS-RADb CBS-RAD–Scanmaxc Differences
Alkoxy radical Bond a
r ∆H0‡ ∆H0‡ r ∆H0‡ ∆rd ∆H0‡e
R1R2CHO· → H· + R1R2C=O
CH3O· C···H 1.956 114.9 95.1 1.80 97.5 –0.16 2.4
CH3CH2O· C···H 1.852 100.6 82.6 1.72 84.6 –0.13 2.0
CH3CH2CH2O· C···H 1.851 98.4 80.6 1.72 82.4 –0.13 1.8
(CH3)2CHO· C···H 1.795 87.1 71.2 1.67 73.2 –0.13 2.0
CH3CH2CH(CH3)O· C···H 1.797 85.6 70.8 1.70 72.4 –0.10 1.6
CH2=CHCH2O· C···H 1.803 85.4 71.8 1.70 73.8 –0.10 2.0
CH2=CHCH(CH3)O· C···H 1.763 80.3 67.1 1.66 69.0 –0.10 1.9
R1R2(CH3)CO· → CH3· + R1R2C=O
CH3CH2O· C···C 2.250 79.2 65.2 2.15 66.5 –0.10 1.3
(CH3)2CHO· C···C 2.182 65.2 55.0 2.10 55.9 –0.08 0.9
CH3CH2CH(CH3)O· C···C 2.192 65.2 57.4 2.13 58.1 –0.06 0.7
(CH3)3CO· C···C 2.148 59.2 52.2 2.09 53.0 –0.06 0.8
R1R2(CH3CH2)CO· → CH3CH2· + R1R2C=O
CH3CH2CH2O· C···C 2.227 61.8 52.9 2.15 53.9 –0.08 1.0
CH3CH2CH(CH3)O· C···C 2.153 47.2 44.6 2.11 45.0 –0.04 0.4
a
Bond being broken in TS.
b
Calculated using B3-LYP/6-31G(d) geometries and (scaled) zero-point vibrational energies.
c
Calculated using the CBS-RAD–Scanmax procedure (see text); ZPVEs obtained with B3-LYP/6-31G(d) at the B3-LYP/6-31G(d) TS geometry.
d
CBS-RAD–Scanmax – B3-LYP/6-31G(d).
e
CBS-RAD–Scanmax – CBS-RAD.

brational energy is held constant at the TS value. The geom-
etry at which the CBS-RAD energy, obtained in this manner,
is a maximum, is an approximation to the CBS-RAD transi-
tion structure, while the corresponding ∆H0‡ represents an
improved CBS-RAD estimate of the barrier. This procedure
has been referred to as Scanmax (37) and is closely related
to the IRCMax procedure of Petersson and co-workers (38).
Table 2 lists the length (r) of the bond being broken in the
TS as obtained with B3-LYP/6-31G(d), the predicted B3-
LYP/6-31G(d), and CBS-RAD values for ∆H0‡ at the B3-
LYP/6-31G(d) optimized geometry, and the values of r and
∆H0‡ obtained using the CBS-RAD–Scanmax procedure. In
each case, the CBS-RAD–Scanmax energy is a maximum at
a value of r shorter than the B3-LYP/6-31G(d) optimized
value, leading to an increase in the predicted ∆H0‡ . The dif-
ferences are listed in the last two columns of Table 2.
Compared with CBS-RAD–Scanmax, B3-LYP/6-31G(d)
overestimates the length of the breaking C—H bonds in the
TS by 0.10–0.16 Å, leading to an underestimation of ∆H0‡
by the standard CBS-RAD procedure by about 1.6–2.4 kJ
mol–1. For C—C bond cleavage the corresponding differ-
ences in r and ∆H0‡ are somewhat smaller, 0.04–0.10 Å and
0.4–1.3 kJ mol–1, respectively. Where available, we use the
CBS-RAD–Scanmax values of ∆H ‡ rather than standard
CBS-RAD values in the remainder of this paper.
We note that a detailed analysis of the dependence of the
results for some of the alkoxy radicals and their C-C uni-
molecular decomposition reaction characteristics on theoreti-
cal level and basis set, at levels comparable to those
employed here, may be found in the study by Somnitz and
Zellner (20). Their work is discussed further below. We note
also that for most of the alkoxy radicals studied here, the
barriers for the β-cleavage reactions have been previously
determined at the CASSCF/6-31G(d) level of theory, without
zero-point energy correction (10). The values so obtained
are uniformly 30–50 kJ mol–1 higher than the values pre-
sented in Tables 3 and 4. In another study of β-scission reac-
tions (39), AM1 theory was used to calculate barriers for a
number of alkoxy radicals, only one of which is common to
the present study. The AM1 barrier for the decomposition of
the tert-butoxy radical decomposition is 13 kJ mol–1 higher
than the CBS-RAD value (Table 3).
Individual alkoxy radicals
We discuss some of the individual alkoxy radicals prior to
examination of the reactivity trends.
Methoxy radical
The CBS-RAD value of the bond dissociation enthalpy
(BDE) of the O—H bond of methanol may be derived from
the data in Table 1. The values at 0 and 298 K are 435.4 and
440.8 kJ mol–1, respectively, in good agreement with experi-
mental values 431 ± 4 and 436 ± 4 kJ mol–1, respectively
(40). Our calculated enthalpies of formation of the methoxy
radical are ∆ f H0o = 28.7 kJ mol–1 and ∆ f H298
o = 21.0 kJ mol–1.
Berkowitz et al. (40) reported ∆ f H0o = 24.7 ± 3.8 kJ mol–1
o = 17.2 ± 3.8 kJ mol–1 while Ramond et al. (36)
and ∆ f H298
o = 21 ± 4 kJ mol–1. Osborn et al. (41) re-
reported ∆ f H300
o
ported ∆ f H0 = 28.5 ± 1.7 kJ mol–1, in close agreement with
our calculated value and also with the recent high-level theo-
retical value of Petraco et al. (19) (∆ f H0o = 27.2 kJ mol–1).
The methoxy radical is predicted to undergo β-scission of
a C—H bond with an Arrhenius activation energy (Ea =
101.1 kJ mol–1 (Table 3)) in close agreement with the value
proposed by Dibble (42) (100 ± 4 kJ mol–1) on the basis of
theoretical and experimental results. The length of the break-
ing C···H bond in the transition structure is 1.80 Å (Table 2),
close to that found by Petraco et al. (19) (1.79 Å). The rate

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 Table 3. Enthalpy barriers (∆H‡, kJ mol–1), free energy barriers (∆G‡, kJ mol–1), frequency factors (A, s–1), activation energies (Ea, kJ mol–1), rate constants (s–1, 298.15 K),
436
reaction enthalpies (∆H, kJ mol–1) and reaction free energies (∆G) for β-scission reactions calculated with CBS-RAD and B3-LYP/6-31G(d).a
‡ ‡
Alkoxy radical Reaction ∆H298 ∆G298 log A Ea kb ∆H0 ∆H298 ∆G298

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55.2

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Methoxy CH3O· → H· + CH2=O 98.6 95.7 13.74 101.1 1.1 × 10–5 79.0 84.8
Ethoxy CH3CH2O· → H· + CH3CH=O 85.1 84.2 13.39 87.6 1.1 × 10–2 57.7 63.1 33.3
1-Propoxy CH3CH2CH2O· → H· + CH3CH2CH=O 83.4 83.3 13.23 85.8 1.6 × 10–2 56.4 62.1 32.3
2-Propoxy (CH3)2CHO· → H· + (CH3)2C=O 74.1 74.3 13.20 76.6 6.0 × 10–1 38.3 44.1 13.0
2-Butoxy CH3CH2CH(CH3)O· → H· + CH3CH2C(CH3)=O 73.1 73.4 13.18 75.6 8.6 × 10–1 39.1 45.5 15.6
Prop-2-en-1-oxy CH2=CHCH2O· → H· + (E)-CH2=CHCH=O 74.7 75.7 13.04 77.2 3.3 × 10–1 46.9 52.3 25.8
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But-3-en-2-oxy CH2=CHCH(CH3)O· → H· + (E)-CH2=CHC(CH3)=O 69.7 70.9 12.99 72.2 2.3 36.4 42.1 16.7
Ethoxy CH3CH2O· → CH3· + CH2=O 67.9 65.8 13.60 70.4 1.9 × 10 40.6 47.8 7.8
2-Propoxy (CH3)2CHO· → CH3· + CH3CH=O 57.7 53.4 13.96 60.1 2.8 × 103 19.8 27.1 –18.5
2-Butoxy CH3CH2CH(CH3)O· → CH3· + CH3CH2CH=O 59.8 59.6 13.25 62.3 2.2 × 102 21.7 28.3 –14.8
tert-Butoxy (CH3)3CO· → CH3· + (CH3)2C=O 54.5 49.7 14.06 56.9 1.2 × 104 9.7 16.4 –33.3
But-3-en-2-oxy CH2=CHCH(CH3)O· → CH3· + (E)-CH2=CHCH=O 48.2 47.1 13.43 50.7 3.6 × 104 13.0 19.4 –19.2
1-Propoxy CH3CH2CH2O· → CH3CH2· + CH2=O 55.7 52.6 13.77 58.1 3.8 × 103 38.1 44.9 –1.2
2-Butoxy CH3CH2CH(CH3)O· → CH3CH2· + CH3CH=O 46.5 43.7 13.72 48.9 1.4 × 105 20.4 26.4 –22.8
Prop-2-en-1-oxy CH2=CHCH2O· → CH2=CH· + CH2=O 92.4 85.0 14.53 94.8 7.9 × 10–3 81.0 87.0 42.7
But-3-en-2-oxy CH2=CHCH(CH3)O· → CH2=CH· + CH3CH=O 83.1 77.3 14.24 85.6 1.8 × 10–1 64.3 69.5 23.2
a
See text for details.
b
298.15 K.

Table 4. Enthalpy barriers (∆H‡, kJ mol–1), free energy barriers (∆G‡, kJ mol–1), frequency factors (A, L mol–1 s–1), activation energies (Ea, kJ mol–1), rate constants
(L mol–1 s–1, 298.15 K), reaction enthalpies (∆H, kJ mol–1), and reaction free energies (∆G) for radical addition reactions calculated with CBS-RAD and B3-LYP/6-31G(d).a
‡ ‡
Radical IEb Reaction ∆H298 ∆G298 log A Ea kc ∆H0 ∆H298 ∆G298
H· 13.6 H· + CH2=O → CH3O· 13.8 40.5 10.37 18.7 1.2 × 107 –79.0 –84.8 –55.2
H· + CH3CH=O → CH3CH2O· 22.0 50.9 9.99 27.0 1.8 × 105 –57.7 –63.1 –33.3
H· + CH3CH2CH=O → CH3CH2CH2O· 21.3 51.0 9.84 26.2 1.8 × 105 –56.5 –62.1 –32.3
H· + (CH3)2C=O → (CH3)2CHO· 30.1 61.3 9.58 35.0 2.8 × 103 –38.3 –44.1 –13.0
H· + CH3CH2C(CH3)=O → CH3CH2CH(CH3)O· 27.6 57.8 9.76 32.6 1.1 × 104 –39.1 –45.5 –15.6
H· + (E)-CH2=CHCH=O → CH2=CHCH2O· 22.4 50.0 10.22 27.4 2.7 × 105 –46.9 –52.3 –25.9
H· + (E)-CH2=CHC(CH3)=O → CH2=CHCH(CH3)O· 27.5 54.3 10.36 32.5 4.6 × 104 –36.4 –42.1 –16.7
Methyl 9.80 CH3· + CH2=O → CH3CH2O· 20.1 58.0 8.41 25.1 1.1 × 104 –40.6 –47.8 –7.8
CH3· + CH3CH=O → (CH3)2CHO· 30.6 71.9 7.81 35.5 3.8 × 10 –19.8 –27.1 18.5
CH3· + CH3CH2CH=O → CH3CH2CH(CH3)O· 31.5 74.4 7.53 36.5 1.4 × 10 –21.7 –28.3 14.8
CH3· + (CH3)2C=O → (CH3)3CO· 38.1 83.0 7.18 43.0 4.4 × 10–1 –9.7 –16.4 33.3
CH3· + (E)-CH2=CHCH=O → CH2=CHCH(CH3)O· 28.8 66.3 8.49 33.8 3.8 × 102 –13.0 –19.4 19.3
Ethyl 8.12 CH3CH2· + CH2=O → CH3CH2CH2O· 10.7 53.8 7.52 15.7 5.9 × 104 –38.1 –44.9 1.2
CH3CH2· + CH3CH=O → CH3CH2CH(CH3)O· 20.1 66.4 6.93 25.0 3.5 × 102 –20.4 –26.4 22.8
Vinyl 8.25 CH2=CH· + CH2=O → CH2=CHCH2O· 5.4 42.3 8.59 10.4 5.9 × 106 –81.0 –86.9 –42.8
CH2=CH· + CH3CH=O → CH2=CHCH(CH3)O· 11.6 52.0 7.97 16.5 1.2 × 105 –64.3 –69.5 –23.2
a
See text for details.
b

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Ionization energy of the radical (in eV).

c
298.15 K.
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Rauk et al.
constant for unimolecular decomposition at 298 K is pre-
dicted to be 1.1 × 10–5 s–1.
The β-scission reaction (eq. [3]) is highly endothermic for
the methoxy radical and the enthalpy change corresponds to
the bond dissociation enthalpy (BDE) of the C—H bond
(∆H0 = 79.0 kJ mol–1 and ∆H298 = 84.8 kJ mol–1 (Table 3)).
Our calculated 0 K value is slightly lower than that deduced
experimentally by Osborn et al. (41) (82.8 ± 1.7 kJ mol–1)
and that calculated by Petraco et al. (19) (84.1 kJ mol–1).
The reverse reaction, addition of H atom to formaldehyde,
has a predicted barrier height at 0 K (∆H0‡ ) of 18.5 kJ mol–1,
in good agreement with the recommended theoretical value
of Petraco et al. (19) (19.7 kJ mol–1). The reverse barrier is
considerably smaller than the forward barrier because of the
endothermicity of the β-scission reaction. Our Arrhenius pa-
rameters are log A = 10.37 and Ea = 18.7 kJ mol–1. The Ea
value is somewhat lower than values reported by Walch (43)
(22 and 26 kJ mol–1), derived experimentally from rates for
deuterium addition at room temperature (log A = 10.30 was
assumed) and an RRKM analysis, respectively. Because of
the large negative entropy of activation calculated for the ad-
dition reaction (–89.6 J mol–1 K–1) the free energy barrier
(∆G298
‡
= 40.5 kJ mol–1) is substantially higher than the
‡
enthalpy barrier (∆H298 = 13.8 kJ mol–1). Our calculated rate
for the addition of H atom to formaldehyde is k = 1.2 ×
107 L mol–1 s–1.
Ethoxy radical
The calculated values for the enthalpy of formation of the
ethoxy radical are ∆ f H0o = 4.2 kJ mol–1 or ∆ f H298
o = –9.9 kJ
–1
mol (Table 1). These are in fair agreement with the values
recommended by Berkowitz et al. (40) (∆ f H0o = –1.7 ±
3.8 kJ mol–1 and ∆ f H298o = –15.5 ± 3.8 kJ mol–1, respec-
tively). We find closer agreement with the experimental
value of Ramond et al. (36) (∆ f H300o = –12 ± 7 kJ mol–1).
Viskolcz and co-workers (15) used a variety of high theoreti-
o = 0 ± 3 kJ mol–1, significantly
cal levels to obtain ∆ f H298
higher than our CBS-RAD value and the experimental
values.
Our calculated barrier for β-scission of the H atom from
‡
the ethoxy radical (∆H298 = 85.1 kJ mol–1) is close to that
obtained by Viskolcz and co-workers (15) (84.8 kJ mol–1) at
the QCISD(T)/6-311+G(3df,2p) level of theory. It is approx-
imately 14 kJ mol–1 lower than for H-atom scission from the
methoxy radical.
The barrier for the reverse reaction, addition of the H
‡ ‡
atom to acetaldehyde (∆H298 = 22.0 kJ mol–1), is somewhat
‡
higher than that for addition to formaldehyde (∆H298 =
13.8 kJ mol–1).
An activation energy of 70.4 kJ mol–1 is predicted for β-
scission of CH3· from the ethoxy radical, which is in close
agreement with a recent experimental determination (Ea =
70.3 kJ mol–1) measured by laser flash photolysis – laser-in-
duced fluorescence (15). Our predicted rate constant (k =
19 s–1) is higher than the experimental values of Viskolcz and
co-workers (14) (5.2 s–1) and Batt and Milne (44) (1.5 s–1).
This reaction has also been investigated by Somnitz and
Zellner (20) at a modified G2 level of theory, using RRKM
theory to derive Arrhenius activation parameters and reaction
rate constants. Their Ea value (73.6 kJ mol–1) is slightly
higher than ours and their derived log A value (12.99) is sig-
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June 9, 2003 2:48:40 PM
437
nificantly lower than ours (13.60). Their predicted rate con-
stant at 300 K (1.46 s–1) is in close agreement with the value
of Batt and Milne (44). β-Scission of the ethoxy radical
yielding CH3· + CH2=O is predicted to be endothermic by
40.6 kJ mol–1 at 0 K and 47.8 kJ mol–1 at 298 K (Table 3).
The experimentally determined activation energy for the
addition of the methyl radical to formaldehyde is 31.0 kJ
mol–1 (11), somewhat higher than that found in the present
calculations (Ea = 25.1 kJ mol–1) (Table 4).
1-Propoxy radical
The predicted values for the enthalpy of formation of
the 1-propoxy radical are ∆ f H0o = –8.2 kJ mol–1 and
o = –29.3 kJ mol–1, considerably less negative than the
∆ f H298
experimental value (∆ f H298o = –41.4 kJ mol–1) (Table 1). In
the light of the good agreement with recent experimental data
(36) observed for other alkoxy radicals, we believe that exper-
imental reexamination for 1-propoxy radical is desirable.
β-Scission of the 1-propoxy radical yielding CH3CH2-
‡
CH=O + H· has a predicted barrier (∆H298 ) of 83.4 kJ mol–1
(Table 3). This value is only slightly lower than that predicted
for β-scission of the H atom from the ethoxy radical (∆H298 ‡
=
85.1 kJ mol ). The 0 K value (∆H0 = 82.4 kJ mol , Table 2)
–1 ‡ –1
is 13.1 kJ mol–1 lower than that calculated by Viskolcz and
co-workers (14) at the B3-LYP/SVP level of theory. The
higher value of Viskolcz is consistent with our observations
that the B3-LYP procedure tends to yield higher values for β-
scission barriers than CBS-RAD (Table 2). The present results
predict that the β-scission reaction of the 1-propoxy radical to
give CH3CH2CH=O + H· is strongly endothermic by 62.1 kJ
mol–1 (∆H298).
The predicted barrier for addition of the H atom to propanal
is 21.3 kJ mol–1 (Table 4) which, not surprisingly, is close to
the value for the addition to acetaldehyde (22.0 kJ mol–1).
The present calculations predict that β-scission of the 1-
propoxy radical yielding CH3CH2· + CH2=O, is impeded by
a barrier (∆H298‡
) of 55.7 kJ mol–1 (Table 3) and is endother-
mic by 44.9 kJ mol–1 (∆H298). This reaction has also been in-
vestigated by Somnitz and Zellner (20). Their RRKM-
derived Ea of 62.4 kJ mol–1 is slightly higher than ours
(58.1 kJ mol–1) and, as in the case of ethoxy, their log A
value (13.25) is somewhat lower than ours (13.77).
‡
Our predicted barrier (∆H298 ) for addition of ethyl radical to
formaldehyde is 10.7 kJ mol–1 (Table 4), approximately 9 kJ
‡
mol–1 lower than that for methyl-radical addition (∆H298 =
–1 –1
20.1 kJ mol ) and approximately 3 kJ mol lower than that
for H-atom addition (∆H298 = 13.8 kJ mol–1).
2-Propoxy radical
The predicted values for the enthalpy of formation of 2-
propoxy radical are ∆ f H0o = –20.9 kJ mol–1 and ∆ f H298
o =
−41.9 kJ mol , somewhat less negative than the experimen-
–1
o = –52.3 kJ mol–1 and ∆ H o = –46 ± 5 kJ mol–1)
tal (∆ f H298 f 300
and the value recommended by Sun and Bozzelli (45)
o = –49.6 kJ mol–1).
(∆ f H298
Loss of the H atom from the 2-propoxy radical by β-
‡
scission is predicted to have a barrier (∆H298 ) of 74.1 kJ
mol , which is close to the G2(MP2) value of 76.5 kJ mol–1
–1
obtained by Devolder et al. (16). It is somewhat lower than
the barriers for H-atom loss from the ethoxy and propoxy
radicals which have only a single α-alkyl substituent (CH3
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438
and CH3CH2, respectively). Conversely, the barrier for addi-
‡ ‡
tion of the H atom to acetone (∆H298 = 30.1 kJ mol–1) is
somewhat higher than that for addition to the aldehydes
‡
CH3CH=O and CH3CH2CH=O (∆H298 = 22.0 and 21.3 kJ
–1
mol , respectively).
β-Scission of the 2-propoxy radical yielding CH3· +
CH3CH=O is predicted to be endothermic, with ∆H0 =
19.8 kJ mol–1 and ∆H298 = 27.1 kJ mol–1 (Table 3). The bar-
rier (∆H298
‡
) is predicted to be 57.7 kJ mol–1. This value is
similar to that found by Viskolcz and co-workers (16) at the
‡
G2(MP2) level (∆H298 = 61.2 kJ mol–1). Our Arrhenius pa-
rameters log A = 13.96 and Ea = 60.1 kJ mol–1, are in mod-
erate agreement with the experimental values, measured by
laser flash photolysis – laser-induced fluorescence (log A =
14.08, Ea = 63.7 kJ mol–1) (16). Our calculated rate at 298 K
is k = 2.8 × 103 s–1, somewhat higher than the experimental
rate (k = 8.3 × 102 s–1). The corresponding theoretical
RRKM values of Somnitz and Zellner (20) are Ea = 62.2 kJ
mol–1, log A = 13.38, and k = 3.53 × 102 s–1 at 300 K, in
somewhat better agreement with the experimental values of
Viskolcz and co-workers (15).
Addition of the methyl radical to acetaldehyde is pre-
‡
dicted to have a significantly higher barrier (∆H298 = 30.6 kJ
–1
mol ) than the addition of the H atom to acetaldehyde
(∆H298
‡
= 22.0 kJ mol–1) or the addition of the methyl radical
‡
to formaldehyde (∆H298 = 20.1 kJ mol–1).
2-Butoxy radical
β-Scission of the 2-butoxy radical may proceed by three
pathways: loss of the H atom, methyl radical, or ethyl radi-
cal. Loss of the H atom entails a very similar barrier
‡
(∆H298 = 73.1 kJ mol–1, Table 3) to that for H-atom loss from
‡
the 2-propoxy radical (∆H298 = 74.1 kJ mol–1). Likewise the
‡
barrier for H atom addition to butan-2-one (∆H298 = 27.6 kJ
–1
mol , Table 4) is similar to that for the addition to acetone
(∆H298
‡
= 30.1 kJ mol–1).
Loss of either of the two alkyl groups, methyl or ethyl, is
hindered by smaller barriers than that for H-atom loss, with
∆H298
‡
= 59.8 and 46.5 kJ mol–1, respectively. Somnitz and
Zellner (20) also investigated the two β-scission pathways in-
volving alkyl group loss. Their theoretical RRKM values
(methyl, ethyl) are Ea = (60.8 kJ mol–1, 50.0 kJ mol–1), log
A = (12.26, 13.15), and k = (46.0 s–1, 2.67 × 104 s–1) at
300 K. Our corresponding values from Table 3 are (methyl,
ethyl) Ea = (62.3 kJ mol–1, 48.9 kJ mol–1), log A = (13.25,
13.72), and k = (2.2 × 102 s–1, 1.4 × 105 s–1) at 298 K. The
Ea values are in good agreement, but the RRKM log A val-
ues are lower than ours and that recommended by Fittschen
et al. (17), who suggest a common value (log A = 14 ± 0.3)
for β C-C scission in alkoxy radicals. Experimental estimates
of the rate constant for the dissociation to the ethyl radical
plus acetaldehyde lie in the range 7.5 × 102 to 3 × 104 s–1
(see reference (20b) for a review and discussion). An experi-
mental investigation in which both channels were observed
found a difference of 11.2 kJ mol–1 between Ea values, and
that the log A value for the ethyl channel was higher by 0.6
(46). Both features are in reasonable agreement with the the-
oretical results.
The barrier for methyl-radical addition to propanal
‡
(∆H298 = 31.5 kJ mol–1) is quite similar to that for the addi-
‡
tion to acetaldehyde (∆H298 = 30.6 kJ mol–1). However, the
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Can. J. Chem. Vol. 81, 2003
barriers for both of these reactions are significantly greater
than for ethyl-radical addition to acetaldehyde (∆H298 =
–1
20.1 kJ mol ). The reaction enthalpies for all three proces-
ses are generally similar (∆H298 = –26.4 to –28.3 kJ mol–1).
tert-Butoxy radical
The present calculations predict that β-scission of the tert-
butoxy radical should occur with a barrier of 54.5 kJ mol–1,
only 3.2 kJ mol–1 lower than for β-scission of the methyl
‡
radical from 2-propoxy radical (∆H298 = 57.7 kJ mol–1).
The calculated Arrhenius parameters for the scission re-
action are log A = 14.06 and Ea = 56.9 kJ mol–1. Ex-
perimentally determined kinetics of tert-butoxy radical de-
composition have been reported by Choo and Benson (11)
(log A = 14.1, Ea = 64 kJ mol–1), Batt et al. (47) (log A =
14.04 ± 0.37, Ea = 62.5 ± 0.6 kJ mol–1), Viskolcz and co-
workers (17) (log A = 14.0, Ea = 60.5 kJ mol–1) and Blitz et
al. (48) (log A = 13.15, Ea = 57 ± 2 kJ mol–1). While our Ea
value is close to that of Blitz et al. (48), their log A value is
significantly lower. Our calculations support a value for A
close to 1 × 1014, which is also recommended by Viskolcz
and co-workers (17).
As noted earlier for the corresponding H-atom additions
to acetone, methyl-radical addition to acetone is hindered by
a significantly higher barrier (∆H298‡
= 38.1 kJ mol–1) than
for the corresponding additions to acetaldehyde and
‡
propanal (∆H298 = 30.6 and 31.5 kJ mol–1, respectively).
Prop-2-en-1-oxy and but-3-en-2-oxy radicals
The two unsaturated oxy radicals, prop-2-en-1-oxy and
but-3-en-2-oxy, may undergo β-scission by losing a vinyl
radical, or by losing a hydrogen atom or a methyl radical, re-
spectively. The structures of the OCCC anticlinal conformers
of these radicals, which are linked to the most stable (also
OCCC anticlinal) conformations of the transition structures
for H loss or CH3 loss, are shown in Fig. 1. In each case, the
<OCCC dihedral angle is such as to orient one of the allylic
groups (H and CH3, respectively) approximately perpendicu-
lar to the plane of the vinyl group and well-positioned for π-
bond-assisted departure.
‡
The barriers (∆H298 ) for H-atom loss from prop-2-en-1-
oxy (74.7 kJ mol ) and but-3-en-2-oxy (69.7 kJ mol–1) radi-
–1
cals are lower than those for the equivalent processes in the
saturated analogues, 1-propoxy (83.4 kJ mol–1) and 2-butoxy
(73.1 kJ mol–1), consistent with π-bond participation in the
β-scission process for the unsaturated radicals. The lower
barrier for the departure of the methyl radical from but-3-en-
2-oxy (48.2 kJ mol–1) as compared to methyl loss from 2-
butoxy (59.8 kJ mol–1) provides additional support for the π-
bond assistance in the former case.
With the exception of H· loss from methoxy, the loss of
vinyl radicals are the most endothermic of those listed in Ta-
ble 3. The barriers for vinyl group loss from the prop-2-en-
1-oxy and but-3-en-2-oxy radicals are ∆H298‡
= 92.4 kJ mol–1
–1
and 83.1 kJ mol , respectively. The higher values for vinyl
radical loss partly reflects the greater endothermicity in
these cases.
Influence of substituents in β-scission reactions
The data in Table 3 are grouped according to the depart-
ing radical (H·, CH3·, CH3CH2·, or CH2=CH·). It is apparent
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Rauk et al.
Fig. 1. The unsaturated prop-2-en-1-oxy and but-3-en-2-oxy radicals.
that within any of these groupings, increasing alkyl substitu-
tion at the site of oxygen attachment promotes β-scission.
Thus the barriers (∆H‡) for β-scission of H· decrease in the
sequence: CH3O· >> CH3CH2O· ≈ CH3CH2CH2O· >
(CH3)2CHO· ≈ CH3CH2CH(CH3)O·. Likewise, the ∆H‡ val-
ues for β-scission of CH3· decrease in the sequence:
CH3CH2O· > (CH3)2CHO· ≈ CH3CH2CH(CH3)O· >
(CH3)3CO·. The two examples of loss of ethyl and vinyl
groups also follow this pattern. These results are all consis-
tent with a decrease in ∆H‡ accompanying a decrease in the
reaction endothermicity ∆H, as expected from the Bell–Ev-
ans–Polanyi relationship. The decreased endothermicity may
in turn be associated with increased hyperconjugative stabi-
lization of the product carbonyl compounds with increased
alkyl substitution.
In addition to the reaction enthalpy effect, the barriers for
β-scission (and for the reverse radical addition to carbonyl,
see below) decrease as the ionization energy of the departing
radical decreases, consistent with the development of posi-
tive charge at the incipient radical in the transition structure.
Our calculated Mulliken charges indeed indicate that there is
a small amount of positive charge of approximately +0.05–
0.07 in the incipient radical moiety in the TS. The low net
charge on the departing radical (H·, CH3·, CH3CH2·, or
CH2=CH·) is consistent with a loose (late) TS with more
than 80% of the net spin on the radical. Interestingly, there
is also a significant polarization of charge in the remainder
of the transition structure, with a negative charge of approxi-
mately –0.4 on the incipient carbonyl oxygen and a positive
charge of approximately +0.3 on the remainder of the mole-
cule. The extent of this polarization increases with increas-
ing alkyl substitution.
Radical addition to the carbonyl group
The addition of radicals to alkenes has been extensively
studied by high-level theoretical calculations (for example,
see refs. 13 and 49). However, the addition of radicals to car-
bonyl compounds has received less attention (for example, see
refs. 19 and 50). This reaction is the reverse of the β-scission
reaction that we have discussed in detail above and we there-
fore make only a few brief comparative remarks here.
Table 4 contains our computed data for radical additions
to carbonyl compounds, grouped according to the radical be-
ing added. An initial comment is that, because of the
endothermicity of the β-scission reactions, the barriers for
the reverse radical addition reactions are considerably
smaller than the β-scission barriers.
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439
Transition structures for the addition of hydrogen, methyl,
ethyl, and vinyl radicals to acetaldehyde are shown in Fig. 2,
along with the calculated Arrhenius activation parameters. A
general plot of the calculated activation energies (Ea) against
reaction enthalpies (∆H298) is displayed in Fig. 3. It is clear
that Ea generally decreases with increasing exothermicity, as
expected from the Bell–Evans–Polanyi relationship. In addi-
tion, for a given exothermicity, the barriers tend to be lower
for radicals with a lower ionization energy. These observa-
tions are qualitatively consistent with the empirical relation-
ship (eq. [4]) of Choo and Benson (11), and with
considerations based on a curve-crossing model (13, 51).
Lower ionization energies enable greater participation of
charge-transfer configurations of the type radical+carbonyl–,
which in turn leads to a lowering of the barrier. The barriers
follow the pattern (CH3)2C=O ≈ CH3CH2C(CH3)=O >
CH3CH=O ≈ CH3CH2CH=O > CH2=O, in line with the re-
action exothermicity. Particularly low barriers are observed
for the highly exothermic additions involving the vinyl
radical.
An interesting observation, already noted above for the
addition of H· to CH2=O, is that, in contrast to the situation
for the β-scission reactions, the ∆G298‡
values for the radical
additions are considerably greater than the ∆H298 ‡
values.
This arises because of substantial negative entropies of acti-
vation, a result that is not unexpected for a bimolecular reac-
tion. The differences between ∆G298 ‡
and ∆H298
‡
depend on
the radical that is added, and increase in the sequence H·
(26–31 kJ mol–1) < CH3· (37–45 kJ mol–1) ≈ CH2=CH· (37–
40 kJ mol–1) < CH3CH2· (43–46 kJ mol–1).
Examination of the log A values shows that the frequency
factors (A) for H· addition are close to 1 × 1010, while those
for alkyl radical addition are two to three orders of magni-
tude smaller. Frequency factors for vinyl-radical addition are
close to those for methyl-radical addition.
Conclusions
The structures of the alkoxy radicals methoxy (CH3O·),
ethoxy (CH3CH2O·), 1-propoxy (CH3CH2CH2O·), 2-propoxy
((CH3)2CHO·), 2-butoxy (CH3CH2CH(CH3)O·), tert-butoxy
((CH3)3CO·), prop-2-en-1-oxy (CH2=CHCH2O·), and but-3-
en-2-oxy (CH2=CHCH(CH3)O·), and the products of their β-
scission reactions, have been determined at the B3-LYP/6-
31G(d) level of theory. CBS-RAD has been used to calculate
o ). The predicted ∆ H o
the enthalpies of formation (∆ f H298 f 298
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440
Fig. 2. Calculated transition structures, bond lengths in (Å), and Arrhenius activation parameters (CBS-RAD, kJ mol–1) for the addition
of hydrogen, methyl, ethyl, and vinyl radicals to acetaldehyde. Distances for hydrogen, methyl, and ethyl addition are by CBS-RAD–
Scanmax; for vinyl group addition, the value is from B3-LYP/6-31G(d) optimization.
Fig. 3. Activation energies for the addition of hydrogen, methyl,
ethyl, and vinyl radicals to carbonyl compounds vs. the reaction
enthalpy.
values agree well with the available experimental data, with
a mean absolute deviation of 5.4 kJ mol–1.
Transition structures (TS) for all the β-scission pathways
were located at the B3-LYP/6-31G(d) level and, in most
cases, at the CBS-RAD–Scanmax level. The bond being
cleaved in the TS tends to be longer with B3-LYP by 0.10–
0.16 Å (C—H) or 0.04–0.10 Å (C—C). At the B3-LYP ge-
ometry, the predicted B3-LYP barriers (∆H0‡ ) are 13–20 kJ
mol–1 higher than the CBS-RAD values for C-H scission,
and 3–14 kJ mol–1 higher for C—C bond breaking. The con-
sequence of not reoptimizing the bond being broken at the
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Can. J. Chem. Vol. 81, 2003
CBS-RAD level is an underestimation of ∆H0‡ by 1.6–2.4 kJ
mol–1 (C—H) or 0.4–1.3 kJ mol–1 (C—C).
Eyring (∆H0‡ , ∆H298
‡
, ∆G298
‡
) and Arrhenius (log A, Ea) ac-
tivation parameters for both the forward (β-scission) and re-
verse (radical addition to carbonyl) pathways were
calculated within the rigid rotor – harmonic oscillator model
and transition-state theory. Most of the available experimen-
tal kinetic data refer to the β-scission pathway. Where direct
comparison was possible, the agreement with the experimen-
tal is very good, generally within 1–5 kJ mol–1 for Ea, and
0.5 for log A.
The values of the barriers for either β-scission or radical
addition to carbonyl are dominated by the reaction enthalpy:
the barrier decreases with decreasing endothermicity (β-
scission) or increasing exothermicity (radical addition). As a
consequence, for example, alkyl or vinyl substituents in the
alkoxy radical lower the barrier for β-scission of H·, CH3·, or
CH3CH2· groups. In addition to the enthalpy effect, the barrier
depends on the ionization energy of the departing radical in
the β-scission reaction (or equivalently, the adding radical in
the radical additions). Smaller barriers are associated with
lower ionization energies. These results are consistent with
expectations based on the curve-crossing model, the smaller
ionization energies allowing greater participation of charge-
transfer configurations of the type radical+carbonyl– in the
transition structure. We find that in the transition structures,
the departing radical carries a small positive charge while
there is substantial charge polarization in the nascent carbonyl
compound, the oxygen atom becoming negatively charged
and the rest of the molecule becoming positively charged.
Acknowledgements
Financial support by the Natural Sciences and Engineering
Research Council of Canada (NSERC), the Australian Re-
search Council (ARC), and the award of Visiting Fellowships
© 2003 NRC Canada
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Rauk et al.
at the Australian National University (to AR, RJB, and SLB)
are gratefully acknowledged. We also thank Professor Allan
East for helpful discussions, and the Multimedia Advanced
Computational Infrastructure (MACI) at the University of
Calgary, the Australian Partnership for Advanced Computing,
and the Australian National University Supercomputer Facil-
ity for generous allocations of computing resources.
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