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Computational Studies on the Keto-Enol Tautomerism of Acetylacetone

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International Journal of Research on Social and Natural Sciences Vol. II Issue 1 June 2017 ISSN (Online) 2455-5916

Journal Homepage: www.katwacollegejournal.com

Computational Studies on the Keto-Enol Tautomerism of

Acetylacetone
Prodyut Roy, Santu Biswas, Anup Pramanik & Pranab Sarkar1
Chemistry, Visva-Bharati University, India

Article Record: Received Mar. 30 2017, Revised paper received May 03 2017, Final Acceptance June 6 2017
Available Online June 7 2017

Abstract

In this article the tautomeric transformation of acetylacetone between its two stable forms, diketo and enol has
been studied theoretically by using Density Functional Theory methodologies. The geometric parameters of the
two tautomers and their relative stabilities in gas phase and in different solvents have been reported and
compared with available experimental and theoretical results. The possible structure for the transition state has
been investigated and the potential energy barriers for the inter conversion between diketo and enolhave been
computed using different level of theories.

Keywords: Acetylacetone, Tautomerism, DFT study, Solvent effect

1. Introduction

The numerous chemical and physical properties of carbonyl compounds are being studied both
theoretically and experimentally by the chemists over many years due to their vast use as organic
reagents. Carbonyl compounds with at least one α-hydrogen atom exist in nature in two different
tautomeric forms at equilibrium, one is ketone and the other is enol. In tautomeric transformation a
proton is shifted from α-carbon atom to the ketonic oxygen atom. However, the equilibrium position
depends on the relative stability of the tautomeric forms. For example, acetaldehyde and vinyl alcohol
remain in tautomeric equilibrium through shifting of a proton from α-carbon atom to the ketonic
oxygen atom, and the presence of these two tautomers in solution has been detected by chemical tests.
Among different carbonyl compounds, β-diketones attract special attention due their properties like-
they are very good chelating ligands. Pentan-2,4-dione [CH3C(O)CH2C(O)CH3], commonly known as
acetylacetone (acac) is the simplest member of the β-diketone family. It is a colourless liquid having
boiling point 1390C, slightly soluble in water, and miscible with organic solvents. It is obtained from
condensation of ethylacetate with acetone. Acetylacetone has a versatile chemical use starting from
the preparation of2,4-dinitro-phenylhydrazone to different kinds of pesticides and at the same time, it
is a good solvent for cellulose acetate and a very good chelating agent for different kinds of metals.
Acetylacetone remains in dynamic equilibrium between its two well-known tautomeric forms through
hydrogen shifting. The equilibrium percentage of these tautomeric forms varies with temperature as
well as the solvent medium. It is reported that, enol form [CH3C(O)CH=C(OH)CH3] predominates
over the β-diketo form in many cases (Lozada-Garcia, 2011). In this tautomeric equilibrium, a
hydrogen atom is shifted from the α-carbon atom between the two carbonyl groups to any one of the
two carbonyl oxygen atoms of the same molecule and vice versa. Despite numerous applicability of
acac, the chemical structure of it is still a matter of debate. Two different structures for the enol form
of acac have been proposed. From the earlier studies it was proposed that, it belongs to a C2V

1
Corresponding Author, E-mail: pranab.sarkar@visva-bharati.ac.in

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International Journal of Research on Social and Natural Sciences Vol. II Issue 1 June 2017 ISSN (Online) 2455-5916

symmetrical structure (Lowrey, 1971), but latter it was observed that it remains in a CS symmetrical
structure as shown in Scheme 1(Srinivasan, 2004). Numerous theoretical and experimental studies
have been carried out on acac, however, the detailed conformational and tautomeric properties of acac
are yet unknown and under investigation.
The enol form of acac is reported to be more stable and it is stabilised by an internal hydrogen bond
referred to as chelated enol (Lozada-Garcia, 2011). From the mid-IR signature of acac, it is indicated
that the main tautomeric form is the chelated enol form but both the diketo and enol forms coexist in
both the liquid and gaseous states (Lozada-Garcia, 2011). NMR studies on acac indicate the strong
predominance of the enol form (81% in pure liquid and 95% in CCl4) (Zielinski, 2002). But in DMSO,
the abundance of enol tautomer is 63% (Zielinski, 2002) and in pure water it is 17% (Bunting, 1995).
The results are in consistence with the observations of the FT-IR study on acac in different solvents,
where it was found that in CCl4the highest concentration of enol form is 86% and in DMSO the
highest concentration of diketo form is 48% (Karabulut, 2012).

Scheme 1: Different tautomeric structures of acetylacetone and their symmetries.

From the gas phase study of acac by Temprado et al.(Temprado, 2005), it has been reported that the
difference in gas-phase enthalpies of formation of the two tautomers isin the range of 20 kJ mol-1. This
observation clearly indicates that the enol form is more volatile and thus its concentration in gas phase
is much higher than that in the liquid phase (81%) (Temprado, 2005).This observation is also
supported by the NMR value reported by Folkendt et al.(Folkendt, 1985). On the basis of measured
enthalpy of vaporisation at 250C, Irving and Wadso also concluded that the amounts of enol tautomers
are 81.4% in liquid acac and 93.3% in gaseous acac (Irving, 1970). Gas-phase electron diffraction
(GED) studies were carried out to determine the symmetry and amount of enol in the equilibria of
acac and it was concluded that the C2v symmetric enol is abundant by 65% at 1000C (Lowrey, 1971).
Later electron diffraction (ED) experiment performed by an ultrafast ED apparatus suggested that the
enolic form possesses CSsymmetry and it is abundant by 78% at 1550C (Srinivasan, 2004). Different
quantum mechanical studies on acac predict the strong predominance of the enol tautomer in the
equilibrium state. Based on complete basis set (CBS) extrapolation procedure; ab initio calculation by
using B3LYP/cc-pVTZ structures results in the tautomerisation enthalpy(∆Henol→keto) value of 3.27
kcal mol-1(Couto, 2006). Another DFT/B3LYP calculation predicts∆G298K =Gketo - Genol =3.95 kcal
mol-1 and presence of only 0.1% of the diketo form i.e. stronger predominance of the enol tautomer
(Sliznev, 2006). All these calculations are based on gas phase equilibrium geometries. But to
understand the effect of solvent polarity on the equilibrium structure and relative thermodynamic
stability, it requires the consideration of solvent effect, which is lack in the literature. Furthermore,
despite numerous studies, the transition state of this keto-enol transformation is not well known. Using

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International Journal of Research on Social and Natural Sciences Vol. II Issue 1 June 2017 ISSN (Online) 2455-5916

different level of computations, it was predicted that the transition state for the hydrogen migration
process bears a C2V symmetrical structure (Broadbent, 2007; Belova, 2014).However, the proton
transfer barrier height and the corresponding TS structure are still in ambiguity. In this paper we
revisit the geometry, electronic structure, and stability of different tautomers of acac in gas phase as
well as in different solvents. At the same time, special emphasis is given on the mechanism of the
tautomerism of acac.

2. Computational Methods

We optimised the geometries and calculated the ground state energies of both the diketo and enol
tautomers of acacwith the help of Density Functional Theory (DFT)employing 6-311G(d) basis sets
for all the atoms and B3LYP as exchange correlation functional as implemented in Gaussian 09 (G09)
package(Frisch, 2009).We then re-optimized the structures by MP2/6-311G(d) method. We also re-
optimized all the structures in different solvents by employing the PCM solvation model as
implemented in G09. Then normal mode frequencies for the optimised geometries were calculated to
check whether they belong to true minima or not. Observing the absence of any negative frequency
for the optimised structures of both the tautomers we confirmed that they were in minimum energy
configurations.

Then we guessed possible structures of the transition states of the tautomeric reaction of acac,
optimised it using same level of theory as discussed above and performed the frequency calculations.
From the single negative frequency of the optimized structure we guess that it might be the transition
state (TS) geometry. Finally, the intrinsic reaction coordinate (IRC) calculations on the proposed TS
structure produced the final geometries of the two tautomers and thus the TS were confirmed. We
estimated the structure of the TS by Synchronous Transit Guided Quasi Newton (STQN) method.
This method uses a linear synchronous transit or quadratic synchronous transit approach to get closer
to the quadratic region around the transition state and then uses a quasi-Newton or eigen value-
following algorithm to complete the optimization. As for minimizations, it performs optimizations by
default using redundant internal coordinates. This method converges efficiently to the actual transition
structure using an empirical estimate of the suitable starting structures.

3. Results and Discussion

3.1 Analysis of the Geometries of Diketo and Enol Forms of Acetylacetone

It is well established that acac exists in both diketo and enol form, enol being more stable in normal
temperature(Lozada-Garcia, 2011; Zielinski, 2002). Although, for many such types of compounds the
diketo formsare more stable than their corresponding enol counterparts, the extra stability of the enol
form, in case of acac, is ascribesd for occupying six membered cyclic structure thereby forming
intramolecular hydrogen bond. The optimized gas phase ground state geometries of both diketone and
enol forms are given in Figure 1(a) and (b), respectively. The geometricparameters of the diketo and
the enol tautomers of acac in gas phase are givenin Table 1.

Figure 1. Optimized geometries of different tautomers of acetylacetone in the gas phase, (a) diketo
and (b) enol form

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From Table 1 it can be observed that the diketo tautomer is nonplanar, the dihedral angle between the
two oxygen atoms (O1, O2) is 139.41⁰, while the enol form is planar, the dihedral angle between the
two oxygen atoms (O1, O2) is 0⁰. The three carbon atoms (C2, C3, and C4), the two oxygen atoms
(O1, O2) and enolic hydrogen atom (H5) remain in the same plane for forming the intra molecular H-
bonding. In the enol form, the distance between the two oxygen atoms is 2.578 Å using B3LYP/6-
311G (d) and 2.617 Å using MP2/6-311G (d) level of theory. These results corroborate well with the
previous studies where it was found that rO-O≈2.55 Å (MP2) and rO-O≈2.63 Å (HF)(Broadbent,2007).
The highly electron correlated CCSD method also resulted an O-O distance of 2.59 Å
(Broadbent,2007). Our computed length of the localised O-H bond is 0.995 [0.984] Å using
B3LYP/6-311G(d) [MP2/6-311G (d)] level of theory. However, the earlier study reported a little bit
elongated (1.018 Å) rO-H while using an additional polarisation function to the basis set (6-31G(d,p))
(Belova, 2014). It is worthwhile to mention here that the geometric parameters are very sensitive to
the size of the basis sets and thus in many cases they are better reproduced with larger basis like aug-
ccpVTZ which on the other hand requires much more computational cost.

From the B3LYP/6-311G(d) computation, the calculated free energy change (∆G)for diketo to enol
transformation is -0.91 kcal mol-1 in gas phase and thus the enol form is predicted to be more stable
(please see Table 2) which corroborates well with the experimental observation (Temprado, 2005).
The calculated enthalpy change (∆H) for the same process is -1.58 kcal mol-1. Previous complete basis
set (CBS) extrapolation procedure; abinitiocalculation by using B3LYP-cc-pVTZ resulted in
tautomerisation enthalpy ∆H

Table 1. Geometricparameters (bond length, ‘r’ in Å; bond angle ‘’and dihedral angle ‘Φ’in ⁰) of
the diketo and the enol tautomers of acetylacetone in the gas phase, using different levels of
computations

Diketo tautomer [Figure1(a)] Enol tautomer [Figure1(b)]

Parameter
B3LYP/ MP2/ B3LYP/ MP2/
6-311G(d) 6-311G(d) 6-311G(d) 6-311G(d)
r(C1-C2) 1.511 1.509 1.513 1.511
r(C2-C3) 1.536 1.529 1.447 1.455
r(C3-C4) 1.537 1.529 1.368 1.368
r(C4-C5) 1.511 1.509 1.494 1.493
r(C2-O1) 1.209 1.218 1.242 1.242
r(C4-O2) 1.209 1.218 1.327 1.332
r(C1-H1) 1.089 1.090 1.089 1.089
r(C1-H2) 1.095 1.095 1.094 1.094
r(C1-H3) 1.094 1.093 1.094 1.094
r(C3-H4) 1.091 1.092 1.083 1.083
r(C3-H5) 1.091 1.092 ----- -----
r(C5-H6) 1.094 1.093 1.094 1.093
r(C5-H7) 1.095 1.095 1.094 1.093
r(C5-H8) 1.089 1.090 1.089 1.090
r(O2-H5) ----- ----- 0.995 0.984
r(O1-H5) ----- ----- 1.688 1.740
r(O1-O2) 4.021 4.007 2.578 2.617
C1C2C3 115.93 115.75 118.26 117.56
C2C3C4 107.87 105.86 121.10 121.39
C3C4C5 115.93 115.75 124.14 124.01
C3C2O1 120.75 120.78 121.96 122.26
C3C4O2 120.75 120.78 122.56 123.21
C2C3H4 108.06 108.45 119.67 119.65

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C4C3H4 111.10 111.39 119.23 118.96

H1C1C2 110.24 109.95 109.72 109.49
H2C1C2 109.81 109.45 110.64 110.25
H3C1C2 110.28 109.98 110.64 110.25
H6C5C4 110.28 109.98 109.84 109.53
H7C5C4 109.80 109.45 109.84 109.53
H8C5C4 110.24 109.95 111.84 111.54
H5O2C4 ----- ----- 106.94 106.72
H1C1H2 109.26 109.54 109.36 109.67
H6C5H7 106.74 107.18 106.96 107.36
Φ(O1C2C3C4) 88.09 89.23 0 0
Φ(O2C4C3C2) 88.16 89.22 0 0
Φ(C1C2C3O1) 177.74 177.32 180.00 180.00
Φ(C5C4C3O2) 177.74 177.30 180.00 180.00
Φ(H5O2C4C3) ----- ----- 0 0
Φ(H5O1C2C3) ----- ----- 0 0
Φ(O1C2C4O2) 138.70 139.41 0 0

(keto→enol) value of -3.27 kcal mol-1(Couto, 2006). From our MP2/6-311G(d) level of computation,
the calculated tautomerisation enthalpy ∆H (keto→enol) value = 3.89kcal mol -1 which is much
deviated from the experimental value of -4.66 kcal mol-1 in the range of temperature 373-445 K
(Folkendt, 1985). So, with the small basis sets like 6-311G with some additional polarisation function,
B3LYP reproduces more accurate thermo chemical data. This is further supported by the recent
experimental and back to back theoretical results (Belova, 2014). Keeping this in our mind, we will
proceed for the solvent phase thermo chemical data with B3LYP/6-311G(d) level of calculations.

As Table 2 shows, like in gas phase, the enol form is predicted to be more stable than the diketo form
in CCl4. However, the diketo form predominates both in water and DMSO. As we have already stated,
the stabilizing factor the enol form is the intra molecular hydrogen bonding, while the diketo form is
stabilized by polar solvent molecules. Thus, in polar protic and aprotic solvents like water and
DMSO, the diketo form is more stable in a conformation with high dipole moment. The higher
stability of diketo form in water is well supported by the experimental observation of Bunting et al.
(Bunting, 1995).

Table 2. Dipole moment, free energy change, enthalpy change and relative stabilityof diketo and enol
tautomers of acetylacetone in gas phase and different solvents

PCM Dipole Frequency More

Method

∆Gdiketo→enol ∆Hdiketo→enol ∆G‡1diketo→enol ∆G‡2enol→diketo

Solvation Species Moment of the TS stable
(kcal mol-1) ( kcal mol-1) ( kcal mol-1) ( kcal mol-1)
Model (Debye) (cm-1) form

Gas Diketo 1.557

-0.91 -1.58 -1890 59.02 59.93 Enol
B3LYP/6-311G(d)

Phase Enol 2.999

Diketo 4.827
In Water 0.93 0.11 -1956 58.52 57.59 Diketo
Enol 3.923
In Diketo 4.778
0.67 -0.16 -1955 58.36 57.69 Diketo
DMSO Enol 3.908
Diketo 1.740
In CCl4 -0.23 -0.97 -1919 58.81 59.05 Enol
Enol 3.374
Gas Diketo 1.824
4.48 3.89 -1949 62.94 58.45 Diketo
Phase Enol 3.525
311G(d)
MP2/6-

Diketo 6.511
In Water 5.93 4.73 -1997 62.53 56.60 Diketo
Enol 4.493
In Diketo 6.473 5.89 4.68 -1996 62.52 56.63 Diketo

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DMSO Enol 4.478

Diketo 2.029
In CCl4 4.73 4.30 -1967 62.54 57.81 Diketo
Enol 3.924

Figure 2. Optimized geometry of the transition state for diketo to enol transformation in gas phase

3.2 Analysis of the Geometry of the Transition State

We have optimised the geometry of the transition state by both of QST2 and QST3 methods which
lead to same transition structure as shown in Figure 2. The corresponding geometric parameters for
the TS structure are given in Table 3.

Table 3. Geometricparameters (bond length, ‘r’ in Å; bond angle ‘’ and dihedral angle ‘Φ’in ⁰)of
the gas phase transition state of the tautomerisation reaction of acetylacetone

QST2 Optimised Geometry

Parameter
(Figure 2)
r(C1-C2) 1.523
r(C2-C3) 1.477
r(C3-C4) 1.455
r(C4-C5) 1.481
r(C2-O1) 1.222
r(C4-O2) 1.267
r(C1-H1) 1.090
r(C1-H2) 1.092
r(C1-H3) 1.095
r(C3-H4) 1.089
r(C3-H5) -----
r(C5-H6) 1.097
r(C5-H7) 1.089
r(C5-H8) 1.092
r(O2-H5) -----
r(O1-H5) -----
r(O1-O2) 3.118
C1C2C3 115.21
C2C3C4 114.96
C3C4C5 -----
C3C2O1 123.94
C3C4O2 108.09
C2C3H4 115.69
C4C3H4 119.13
H1C1C2 109.10
H2C1C2 112.60

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H3C1C2 109.23
H6C5C4 106.86
H7C5C4 112.29
H8C5C4 110.72
H5O2C4 -----
H1C1H2 110.00
H6C5H7 109.27
Φ(O1C2C3C4) 5.54
Φ(O2C4C3C2) 84.12
Φ(C1C2C3O1) 179.65
Φ(C5C4C3O2) 175.76
Φ(H5O2C4C3) -----
Φ(H5O1C2C3) -----
Φ(O1C2C4O2) 70.59

From Table3 it is evident that, as expected, the TS structure is in between the diketo and the enol
form. The dihedral angle Φ(O1C2C4O2)is 70.59⁰whichis reduced to approximately half of that in the
diketo tautomer. Thus, the nonplanar diketo form converts to the planar enol form by changing its
dihedral angles by rotating the C2-C3 σ-bond. From the frequency computation it is observed that it
has a single negative frequency of -1890 cm-1 using B3LYP functional in gas phase. In different
solvent phases, this value does not change so much indicating a characteristic frequency of C-H bond.
In particular, this vibrational frequency corresponds to the C3-H5 bond vibration frequency. So it is
clear that tautomeric transformation, in case of acac, is occurred through this degree of freedom. From
the IRC calculation we found the final geometries are close to the optimised geometries of the two
forms of acac. The energy of this TS structure is higher in comparison to that of the diketo form by
59.02kcal mol-1 and from the enol form by 59.93 kcal mol-1. Thus, the potential energy barrier for the
diketo to enol transformation is 59.02kcal mol-1 and that of the reverse process is 59.93kcal mol-1. So,
diketo to enol transformation is more feasible than the reverse transformation and hence the
population of the enol form should be higher as predicted from the previous experimental and
theoretical studies (Lozada-Garcia, 2011).

In aqueous medium, as we have already stated, the overall stability of the diketo tautomer is
increased, however, the TS barrier height is reduced to some extent. This indicates that, in aqueous
medium the tautomeric equilibrium is shifted towards diketo form but the dynamic equilibrium is
reached faster. In other aprotic solvents, the trend is not unique, however, in any case, the barrier
heightsare reduced. Noteworthy, the characteristics of TS structure are not affected too much by
solvation.

4. Conclusions

We have studied the keto-enol tautomerisation reaction of acetylacetone by the density functional
theory method in gas phase as well as in different solvents. We have found that in the gas phase, the
tautomerisation enthalpy of the enol to diketo transformation is1.58 (-3.89) kcal mol-1 using B3LYP
(MP2) level of theory. Thus, the enol form is the more stable form of acetylacetone and the population
of the enol form should be higher in gas phase as evidenced from previous experimental observations.
Like in gas phase, also the enol tautomer is found to be more abundant. The higher concentration of
the enol tautomer in gas phase and in CCl4 may be due to its more volatile nature and there involves a
strong intramolecular hydrogen bonding.However, in the solvent phase the ratio of the diketo and enol
tautomer depends solely on the solvent polarity. In polar protic solvent (water) and polar aprotic
solvent (DMSO) the diketo tautomer predominates. This may be due to higher dipole moment of the
diketo form in polar solvents. The higher concentration of the diketo form in water is supported the
previous experimental observation.

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Acknowledgments

The authors sincerely acknowledge UGC and DST, Govt. of India for providing financial supports.
P.R. sincerely acknowledges DST-INSPIRE Scholarship.

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