RAPID COMMUNICATIONS IN MASS SPECTROMETRY

Rapid Commun. Mass Spectrom. 12, 1697–1700 (1998)

Keto–Enol Tautomerism and Dissociation of

Ionized Acetaldehyde and Vinyl Alcohol.
A G2 Molecular Orbital Study
W. Bertrand and G. Bouchoux*
Département de Chimie, Laboratoire des Mécanismes Réactionnels, UMR 7651, Ecole Polytechnique, 91128 Palaiseau cedex,
France

Part of the potential energy surface for ionized vinyl alcohol, [CH2=CHOH]
‡, 1
‡, acetaldehyde,
[CH3CHO]
‡, 2
‡, and hydroxycarbene [CH3COH]
‡, 3
‡, is calculated at the G2 level of theory. It is
confirmed that the latter structure is a stable species (predicted 298K heat of formation = 835 kJ/mol) which
serves as intermediate during dissociation of 1
‡ and its isomerization to 2
‡. # 1998 John Wiley & Sons,
Ltd.
Received 7 September 1998; Revised 26 September 1998; Accepted 27 September 1998

In 1984, two theoretical studies were devoted to the keto–
enol tautomerism of [C2H4O]
‡ radical cations.1,2 In both
cases geometry optimization was conducted at the Hartree–
Fock level with a simple 3-21G or 4-31G basis set and
electron correlation effects were taken into account by
single point calculations on these geometries. The common
conclusion of these studies was that, in addition to ionized
vinyl alcohol, [CH2=CHOH]
‡, 1
‡, and acetaldehyde,
[CH3CHO]
‡, 2
‡, a third structure, the hydroxycarbene
[CH3COH]
‡, 3
‡, plays an important role in the chemistry
of this system. The various isomerization routes and the
dissociations by H atom loss, involving 1
‡, 2
‡ and 3
‡,
depicted in Scheme 1, were explored.
Both studies1,2 agree qualitatively in the estimates of the
various critical energies separating each isomer and the
dissociation products. However discrepancies of no less
than 50 kJ/mol were apparent for some elementary steps,
particularly hydrogen atom migrations. Furthermore, con-
flicting conclusions were drawn concerning the nature of the
energy determining step for dissociation3 of 1
‡. To clarify
these questions, in view of the moderate size of this system,
it was of interest to reinvestigate the energetic of reactions
of Scheme 1 using a more sophisticated theoretical method
such as the G2 theory.4
COMPUTATIONAL SECTION
It seems well established that accurate heats of formation of
open-shell systems can be attained at the G2 level of
theory4a for species with low spin contamination.5 Standard
G2 theory employs a geometry optimized at the MP2(full)/
6-31G(d) level and a scaled HF/6-31G(d) ZPE. A base
energy calculated at the MP4/6-311G(d,p) level is corrected
by several additivity approximations to QCISD(T) and to 6-
311‡G(3df,2p) basis set. In an attempt to account for
residual basis set deficiencies, G2 theory introduces higher-
level corrections (HLC) that depends on the number of
paired and unpaired electrons. In the more economical
*Correspondence to: G. Bouchoux, Département de Chimie, Labor-
atoire des Mécanismes Réactionnels, UMR 7651, Ecole Polytech-
nique, 91128 Palaiseau cedex, France.
G2(MP2) approach, the basis set-extension energy correc-
tions are obtained at the 2nd order Molle–Plesset level.4b
Standard ab initio calculations have been carried out
using the Gaussian-94 series of programs.6 The MP2(full)/
6-31G(d) optimized geometries of the different structures
included in this study are schematized in Fig. 1. The
corresponding G2 and G2(MP2) relative energies are
presented in Table 1.
Two general remarks can be made at this stage. In the
present investigation spin unrestricted wave functions were
used for the HF calculation. For the species considered here,
the unprojected <S2> values were within 0.757–0.890
indicating moderate spin contamination (Table 1). It is thus
expected that the G2 theory provides reasonable relative
energies for the open-shell system considered here. The
second point to mention is the systematic agreement
obtained for the relative energies calculated either at the
G2 or the G2(MP2) levels of theory.
RESULTS AND DISCUSSION
Stable species
The MP2/6-31G* optimized geometries of ionized vinyl
alcohol, 1
‡, and acetaldehyde, 2
‡, have been reported
earlier.7,8 We confirm that ionized vinyl alcohol is more
stable in its anti- conformation, probably due to a favourable
electrostatic interaction between the oxygen atom and the
nearest H atom of the methyl group (H6, Fig.1). The most
stable conformer of ionized acetaldehyde exhibits also a cis-
coplanar HCCO arrangement developing an electrostatic
attraction between the oxygen atom and one H of the methyl
group (H5, Fig.1). It is noteworthy that the eclipsed HCCH
conformer corresponds to a transition structure for the
rotation of the methyl group, for which the critical energy
calculated at the MP2/6-31G* level is 4.7 kJ/mol. Ionized
hydroxycarbene, 3
‡, has been characterized at the HF/4-
31G level by Bouma et al.9 The present results show that the
most stable conformation of this ion exhibits also a
favourable interaction between the oxygen atom and one
H of the CH3 moiety (H5, Fig.1). The transition structure for

CCC 0951–4198/98/221697–04 $17.50 # 1998 John Wiley & Sons, Ltd.

1698 G2 MO STUDY OF C2H4O
‡ SYSTEM

Figure 1. MP2(full)/6-31G(d) optimized geometries of the [C2H4O]
‡ structures considered (bond

lengths in Å, bond angles in degrees).

Rapid Commun. Mass Spectrom. 12, 1697–1700 (1998) # 1998 John Wiley & Sons, Ltd.
 G2 MO STUDY OF C2H4O
‡ SYSTEM 1699

Table 1. Calculated relative energies (kJ/molÿ1) of the [C2H4O]
‡ structures considered

Species HF/6-31G*a MP2(full)/6-31G*b <S2>c G2(MP2)d G2e
1
‡ 0 0 0.765 0 0
2
‡ 39 80.6 0.775 56.2 55.4
3
‡ 74 70.9 0.757 67.7 68.1
4
‡ 135 67.7 0.750 103.4 104.7
TS 1/2 299 251.2 0.813 214.7 215.0
TS 1/3 238 221.1 0.764 183.5 183.5
TS 2/3 294 248.6 0.789 210.6 210.9
TS 2/4 190 143.4 0.820 113.1 112.8
TS 3/4 261 220.5 0.890 188.7 188.6
a
E(1
‡) = ÿ152.608941 Hartrees.
b
E(1
‡) = ÿ153.014403 Hartrees.
c
At the MP2(full)/6-31G* level.
d
E(1
‡) = ÿ153.210369 Hartrees.
e
(1
‡) = ÿ153.214087 Hartrees.

rotation of the methyl group is the HCCO trans-coplanar
conformation which lies 2.2 kJ/mol above 3
‡.
At the G2 level, the calculated 298 K relative enthalpies
of 1
‡, 2
‡ and 3
‡ are 0, 56 and 68 kJ/mol respectively; the
energy level of the dissociation products [CH3CO]‡ ‡ H
,
4
‡, is calculated to be 105 kJ/mol above 1
‡ (Table 1). A
comparison between the data quoted in Table 1 and Table 2
shows an excellent agreement between calculated and
experimental relative energies for 1
‡, 2
‡ and the
dissociation products 4
‡ but not for 3
‡, for which a
discrepancy of no less than 30 kJ/mol is observed.
Some comments may be made about these results. The
298 K heat of formation of 1
‡, determined by photoioniza-
tion threshold measurement10 and G2(MP2) calculated
isodesmic and isogyric reaction enthalpy,7 agree to within
3 kJ/mol. The experimental value, 768 kJ/mol, slightly
higher than the tabulated one (757 kJ/mol),11 is accurate
to within  5 kJ/mol.10 The heat of formation of ionized
acetaldehyde 2
‡, 821 kJ/mol, is derived from the heat of
formation and the ionization energy of the neutral,11 and the
uncertainty in DfH°[2
‡] is less than 1 kJ/mol. The
experimental heat of formation of ionized hydroxycarbene,
3
‡, has been obtained from the appearance energy of m/z
44 ions from pyruvic acid, CH3COCOOH. Several sources
of uncertainities on this determination allow the authors to
propose a rough estimate of 865  20 kJ/mol. This leads to a
relative energy of 3
‡, with respect to 1
‡ equal to 97  25
kJ/mol. The difference observed between this value and our
Table 2. Experimental thermochemical data (kJ/molÿ1)
DfH°298
Species
768  5a
1
‡ 765b
757c
2
‡ 821  1c
3
‡ 865  20d
CH3CO‡ ‡ H
657e (653c) ‡ 218c
a
From photoionization threshold energy determination, Ref. 10.
b
Theoretical estimate from G2(MP2) calculations, Ref. 7.
c
From the tabulation of Ref. 11.
d
From Ref. 13.
e
From Ref. 12.
theoretical estimate (68 kJ/mol at both the G2 and G2(MP2)
levels) is thus not completely unexpected. In view of the
good agreement between G2 calculation and experiment
obtained for the other species considered here, we can
consider that in this case the theory is closer to the reality.
Consequently, a heat of formation value may be proposed
for ionized hydroxycarbene 3
‡ by combining the experi-
mental heat of formation of ionized vinyl alcohol, 1
‡, or
ionized acetaldehyde, 2
‡, and the G2 relative energies of
1
‡–3
‡. Using DfHo[CH2=CHOH]
‡ = 768 kJ/mol,
DfH°[CH3CHO]
‡ = 821 kJ/mol, together with the data
quoted in Table 1, this leads to DfH°[CH3COH]
‡ = 835 kJ/
mol.
Potential energy diagram
The portion of the potential energy surface associated with
Scheme 1 is presented in Fig. 2. It is in qualitative
agreement with the previous works mentioned above and
provides the following conclusions.
The transition structures for 1,2- or 1,3-hydrogen
migrations and that for the H loss from 3
‡, lie in a very
narrow energy range (182 to 215 kJ/mol). This finding is
comparable with that reported previously, but the critical
energies calculated at the G2 level are well below that of
Ref. 1 (by ca. 50 kJ/mol) or Ref. 2 (by ca. 20 kJ/mol).
The behaviour of each stable species may be now briefly
summarized. Starting from 1
‡, the lowest energy route is
its isomerization to ionized hydroxycarbene 3
‡ which may
in turn dissociate to [CH3CO]‡ ‡H
, 4
‡. Both steps need
comparable energies (182 and 189 kJ/mol for 1/3
‡ and 3/
4
‡ respectively) and it is difficult to say which is really the
DH°298 energy determining step of the overall process. The
transition structure for H loss from 3
‡ is calculated to be
0 85 kJ/mol above the products [CH3CO]‡ ‡H
, 4
‡. We note
that this value is less than the estimate given by Burgers et
53 al.3 for the recombination of [CH3CO]‡ ‡H
(120 kJ/mol),
97 but this latter, deduced from the appearance energy
107
determination of [CH3CO]‡ from pyruvic acid, is certainly
an upper limit due to kinetic shift effects.
Isomerization of vinyl alcohol 1
‡ to acetaldehyde 2
‡
may follow either a direct 1,3-hydrogen migration (critical
energy 215 kJ/mol) or two successive 1,2-hydrogen shifts
1
‡ → 3
‡ → 2
‡ (overall critical energy 211 kJ/mol). In
fact, both processes cannot compete with the hydrogen atom
loss which needs only 189 kJ/mol. This is in agreement with

# 1998 John Wiley & Sons, Ltd. Rapid Commun. Mass Spectrom. 12, 1697–1700 (1998)
1700 G2 MO STUDY OF C2H4O
‡ SYSTEM
Figure 2. Potential energy diagram for the isomerization/dissociation processes of [C2H4O]
‡
ions (G2 calculations).
deuterium labelling experiments which show that the
hydroxylic hydrogen is specifically eliminated from 1
‡.
The behaviour of ionized acetaldehyde 2
‡ is dominated
by the specific elimination of the aldehydic hydrogen atom.
This is fully understandable from the potential energy
diagram of Fig. 2. The dissociation 2
‡ → 4
‡ needs only 58
kJ/mol while the two possible isomerization processes
starting from 2
‡ need ca. 160 kJ/mol. Note that our G2
results indicate a reverse activation barrier of 9 kJ/mol for
the H atom loss 2
‡ → 4
‡, confirming the conclusions of
Smith and Radom8 based on G1 calculations.
In summary, the G2 calculations presented above provide
a quantitative picture of the thermochemistry of the most
simple keto–enol tautomerism of cation radicals. The
stability and the crucial role of ionized hydroxycarbene,
[CH3COH]
‡ in the chemistry of this system is fully
confirmed. Moreover, a 298 K heat of formation value of
835 kJ/mol is proposed for this species.
REFERENCES
1. G. Bouchoux, J. P. Flament and Y. Hoppilliard, Int. J. Mass
Spectrom. Ion Processes 57, 179 (1984).
2. Y. Apeloig, M. Karni, B. Ciommer, G. Depke, G. Frenking, S.
Meyn, J. Schmidt and H. Schwarz, Int. J. Mass Spectrom. Ion
Processes 59, 21 (1984).
Rapid Commun. Mass Spectrom. 12, 1697–1700 (1998)
3. P. C. Burgers, J. K. Terlouw and J. L. Holmes, Int. J. Mass
Spectrom. Ion Processes 65, 91 (1985).
4. (a) L. A. Curtiss, K. Raghavachari, G. W. Trucks and J. A. Pople, J.
Chem. Phys. 94, 7221 (1994). (b) L. A. Curtiss, K. Raghavachari
and J. A. Pople, J. Chem. Phys. 98, 1293 (1993).
5. P. M. Mayer, C. J. Parkinson, D. M. Smith and L. Radom, J. Chem.
Phys. 108, 604 (1998).
6. M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G.
Johnson, M. A. Robb, J. R. Cheesemann, T. A. Keith, G. A.
Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham,
V. G. Zakrewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B.
Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y.
Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R.
Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J.
Baker, J. P. Stewart, M. Head-Gordon, C. Gonzales and J. A.
Pople, Gaussian 94 Revision, Gaussian, Inc., Pittsburgh, PA, 1995.
7. F. Turecek and C. J. Cramer, J. Am. Chem. Soc. 117, 12243 (1995).
8. B. J. Smith and L. Radom, Int. J. Mass Spectrom. Ion Processes
101, 209 (1990).
9. W. J. Bouma, J. K. MacLeod and L. Radom, J. Am. Chem. Soc.
101, 5540 (1979).
10. G. Bouchoux, C. Alcaraz, O. Dutuit and M. T. Nguyen, Int. J. Mass
Spectrom. Ion Processes 137, 93 (1994).
11. S. G. Lias, J. E. Bartmess, J. F. Liebman, J. L. Holmes, R. D. Levin
and W. G. Mallard, J. Phys. Chem. Ref. Data, Suppl. 1, 17 (1988).
12. J. C. Traeger, R. G. McLoughlin and A. J. C. Nicholson, J. Am.
Chem. Soc. 104, 5318 (1982).
13. J. K. Terlouw, J. Wezenberg, P. C. Burgers and J. L. Holmes, J.
Chem. Soc. Chem. Commun. 1121 (1983).
# 1998 John Wiley & Sons, Ltd.