Kinetic aspects of the effect of CO pressure and methanol concentration on cyclohexene hydrocarbomethoxylation in the presence of the Pd(PPh 3)2Cl2-PPh3-p-toluenesulfonic acid catalytic system

Article abstract of DOI:10.1134/S0965544113010027

The dependence of the rate of the cyclohexene hydrocarbomethoxylation reaction catalyzed by the Pd(PPh₃)₂Cl₂-PPh ₃-p-toluenesulfonic acid system on the CO pressure and methanol concentration at temperatures varied in the range of 358-388 K has been investigated. The data are interpreted in terms of the previously proposed mechanism involving as intermediates ion pairs containing cationic hydride, alkyl, and acyl palladium complexes. By the least squares technique, apparent constants relating to the effect of CO pressure and methanol concentration have been estimated for the rate equation derived earlier. The apparent activation energies have been determined for these constants, and the following stability series of palladium complexes has been proposed on their basis: Pd(PPh ₃)₂ (CO)₂ > Pd(PPh₃)₄ > Pd(PPh₃)₂ (CH₃OH)₂ > H Sol⊕ [Pd(PPh₃)₂ (Cl)(Sol)].

Full text of DOI:10.1134/S0965544113010027

ISSN 0965ꢀ5441, Petroleum Chemistry, 2013, Vol. 53, No. 1, pp. 39–45. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © V.A. Aver’yanov, N.T. Sevost’yanova, S.A. Batashev, A.M. Demerlii, 2013, published in Neftekhimiya, 2013, Vol. 53, No. 1, pp. 43–49.
Kinetic Aspects of the Effect of CO Pressure and Methanol
Concentration on Cyclohexene Hydrocarbomethoxylation
in the Presence of the Pd(PPh3)2Cl2–PPh3–pꢀToluenesulfonic Acid
Catalytic System
V. A. Aver’yanov, N. T. Sevost’yanova, S. A. Batashev, and A. M. Demerlii
Department of Organic and Biological Chemistry, State Teacher Training University of Tula, Tula, Russia
eꢀmail: piligrim.tula.ru@gmail.com
Received June 7, 2012
Abstract—The dependence of the rate of the cyclohexene hydrocarbomethoxylation reaction catalyzed by
the Pd(PPh3)2Cl2–PPh3–pꢀtoluenesulfonic acid system on the CO pressure and methanol concentration at
temperatures varied in the range of 358–388 K has been investigated. The data are interpreted in terms of the
previously proposed mechanism involving as intermediates ion pairs containing cationic hydride, alkyl, and
acyl palladium complexes. By the least squares technique, apparent constants relating to the effect of CO
pressure and methanol concentration have been estimated for the rate equation derived earlier. The apparent
activation energies have been determined for these constants, and the following stability series of palladium
complexes has been proposed on their basis:
ꢀ
ᮎ
Pd(PPh3)2(CO)2 > Pd(PPh3)4 > Pd(PPh3)2(CH3OH)2 > HSol[Pd(PPh3)2(Cl)(Sol)]
.
Keywords: hydrocarbalkoxylation, cyclohexene, methylcyclohexanecarboxylate, palladium compounds,
hydride complexes, rate equation, intermediates
DOI: 10.1134/S0965544113010027
In [1–4], it was shown that studying the effect of evant parameters of the rate equation, and estimated
the enthalpies of the formation of the [Pd(PPh3)4] and
temperature on the rate of the hydrocarbalkoxylation
reaction opens the possibility of determining the actiꢀ
vation parameters of apparent constants of rate equaꢀ
tions and these data in conjunction with the results of
direct kinetic experiments on the chemical behavior of
certain suggested intermediates make it possible to
compile a database of rate constants for the elemenꢀ
tary steps of carbonylation reactions and their enthalꢀ
pies and activation energies. The earlier studies of the
effect of temperature on the dependence of the rate of
the cyclohexene hydrocarbalkoxylation reaction with
cyclohexanol upon the concentration of the reactants
and catalyst components (Pd(PPh3)2Cl2 and tripheꢀ
nylphosphine) enabled us to determine the apparent
activation energy for some of the kinetic parameters
and to estimate on their basis the enthalpies of the forꢀ
mation of the Pd complexes Pd(PPh3)2(C6H11OH)2,
ꢀ
ᮎ
HSol[Pd(PPh3)2(Cl)(Sol)]
complexes from
Pd(PPh3)2Cl2 [5]. In this paper, we present the results
on the effect of temperature on the apparent rate conꢀ
stants for cyclohexene hydrocarbomethoxylation
O
t, P, cat
+ CO + CH3OH
C
OCH3
in the presence of the Pd(PPh3)2Cl2–PPh3–pꢀtolueneꢀ
sulfonic acid (TsOH) catalyst system that reflect the
contribution of carbon monoxide and methanol to the
rate of this reaction.
EXPERIMENTAL
Pd(PPh3)2(CO)2,
and
Pd(PPh3)4
from
The cyclohexene hydrocarbomethoxylation reacꢀ
tion was studied in the batch reactor described in [6].
All experiments were carried out in toluene. The reacꢀ
tion mass was analyzed by GLC using oꢀxylene as an
internal standard; the analytical procedure is detailed
in [5]. The details of the kinetic experiments are given
Pd(PPh3)2(C6H5CH3)2 [4]. In continuation of these
studies, we investigated the influence of temperature
on the dependence of the rate of the cyclohexene
hydrocarbomethoxylation reaction upon the concenꢀ
trations of Pd(PPh3)2Cl2 and free triphenylphosphine,
determined the apparent activation energies of the relꢀ in [7]. The accuracy of determining the reactant and
39

40
AVER’YANOV et al.
product concentrations was 3%. Confidence interꢀ The curves for the dependence of reaction rate r0 upon
vals for the kinetic parameters determined are given in
the text.
[
CH3OH] are also nonmonotonic, having a maximum
at 0.15 to 0.20 mol/L CH3OH
.
Based on the data of previous experiments on the
effect of the reactants and the components of the catꢀ
alytic system (Pd(PPh3)2Cl2–PPh3–TsOH) on this
reaction at a fixed temperature, we found that the
reaction is first order in cyclohexene and TsOH, chloꢀ
ride anions inhibit the reaction, the reaction is insenꢀ
sitive to tosylate anions, and the methanol concentraꢀ
tion and CO pressure dependences of the reaction rate
are nonmonotonic [7]. These data were interpreted in
terms of a mechanism that involves as catalytic cycle
intermediates ion pairs of cationic hydride, alkyl, and
acyl palladium complexes with tosylate anions
RESULTS AND DISCUSSION
To reveal the effect of temperature on the depenꢀ
dence of the cyclohexene hydrocarbomethoxylation
rate upon the CO pressure, five sets of experiments in
the temperature range of 368–388 K were performed
with varying the CO pressure in each set from 0 to
6.1 MPa. Figure 1 presents the data obtained in these
experiments as plots of the initial reaction rate versus
рСО for different temperatures. These curves are nonꢀ
monotonic in character for all of the temperatures.
Similar experiments were conducted on the effect
of methanol concentration on the rate of hydrocarꢀ
bomethoxylation at different temperatures (Fig. 2). (Scheme 1):
k0
PdCl2(PPh3)2 + CH3OH
Pd(PPh3)2 + CH2O + 2HCl
(1)
(2)
k1
Pd(PPh3)2 + 2Sol
(X0)
Pd(PPh3)2 (Sol)2
(X1)
k–1
ꢀ
ᮎ
k2
Pd(PPh3)2 (Sol)2 + TsOH
(X1)
[HPd(Sol)(PPh3)2]TsO + Sol
(X2)
(3)
k–2
ᮎ
[HPꢀd(PPh3)2]TsO + Sol
[HPꢀd(Sol)(PPh3)2]TᮎsO +
(X2)
k3
k–3
(X3)
(4)
k4
(5)
k7
k–4
slow
C OCH3
ᮎ
ᮎ
ꢀ
ꢀ
Pd(Sol)(PPh3)2
TsO
O
(8)
(X4)
k–5
k5
(6)
+ CH3OH
+ CO
ᮎ
Pꢀd(CO)(PPh3)2
(X5)
ᮎ
k–6
k6
ꢀ
.
CO Pd(Sol)(PPh3)2
TsO + Sol
TsO
(X6)
(7)
where Sol stands for solvent (toluene) molecules.
Scheme 1.
The nonmonotonic character of the reaction rate anol concentrations and the CO pressure can be interꢀ
dependence on the triphenylphosphine [5] and methꢀ preted in terms of the ligand exchange equilibriums:
k8
Pd(PPh3)2(Sol)2 + 2PPh3
(X1)
Pd(PPh3)4 + 2Sol,
(X7)
(9)
k–8
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KINETIC ASPECTS OF THE EFFECT OF CO PRESSURE
41
3
3
r
· 10 , mol/(L min)
r
· 10 , mol/(L min)
0
0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
5
4
3
5
4
3
2
1
2
1
0
0
1
2
3
4
5
· 10 , Pa
6
0.2
0.4
0.6
0.8
1.0
–6
Р
СО
[CH OH], mol/L
3
Fig. 2. Effect of methanol concentration on the initial rate
Fig. 1. Effect of CO pressure on the initial rate of the cycloꢀ
of the cyclohexene hydrocarbomethoxylation reaction at
hexene hydrocarbomethoxylation reaction at temperaꢀ
6
tures of (1) 368, (2) 373, (3) 378, (4) 383, and (5) 388 K.
Р
= 2.1
×
10 Pa and temperatures of (
1) 358, (
2) 363,
СО
Concentrations, mol/L: [C H ] = 0.1, [CH OH] = 0.45,
6
10
–3
3
(
3
) 368, (
4
) 373, and (
5
) 378 K; concentrations, mol/L:
3
[Pd(PPh ) Cl ] = 2.0
×
10 , [PPh ] = 8.0
×
10⎯
,
–3
[C H ] = 0.1, [Pd(PPh ) Cl ] = 2.0
×
10 , [PPh ] =
3
3 2
2
3
6
10
3 2
2
–2
–2
–3
[TsOH] = 2.4
×
10
.
8.0 × 10 , [TsOH] = 2.4 × 10 .
k9
k–9
Pd(PPh3)2(Sol)2 + CO
(X1)
Pd(CO)(PPh3)(Sol)2 + PPh3,
(X8)
(10)
k10
Pd(PPh3) (Sol)2 + CH3OH
Pd(CH3OH)(PPh3)(Sol)2 + PPh3,
(X9)
(11)
(12)
(13)
(X12)
k–10
k11
Pd(PPh3) (Sol)2 + 2CH3OH
Pd(PPh3)2(CH3OH)2 + 2Sol,
(X10)
(X12)
k–11
k12
Pd(PPh3) (Sol)2 + 2CO
Pd(PPh3)2(CO)2 + 2Sol.
(X11)
(X1)2
k–12
However, we believe that the observed decline in tion of the inactive complex X12 from X1 by the
the specific catalytic activity of the precursor with action of HCl produced from Pd(PPh3)2Cl2 in reacꢀ
an increase in its concentration is due to the formaꢀ tion (1) [5]:
ꢀ
ᮎ
k13
HCl + Pd(PPh3)2Sol2
(X1)
HSol[Pd(PPh3)2(Cl)Sol] .
(X12)
(14)
k–13
The inactivity of Х12 is caused by the anionic charꢀ the alcohol molecule at the acyl carbon atom in the Х6
acter of its Pdꢀcontaining moiety. On the other hand,
the factor responsible for the formation of Х12 type
complexes is a higher ability of the chloride ion to
coordinate to the central palladium atom compared
with the acetate or tosylate anion [8–10].
complex. The arguments in favor of this point of view
are presented in [9–13]. In this context, all the preꢀ
ceding reversible steps can be considered quasiꢀequiꢀ
librium. Then the reaction rate can be expressed by the
equation:
In [9, 11] it was shown that the rateꢀdetermining
step of the catalytic cycle is the nucleophilic attack of
(15)
r = k7[X6][CH3OH].
PETROLEUM CHEMISTRY Vol. 53
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42
AVER’YANOV et al.
In the case of formation of the complex Х12, the
and
amount of bound and free HCl can be comparable.
Then the expression of К13 takes the following form:
143 7 kJ mol
= 10−14.84 exp
,
e
⎛
⎜
⎝
⎞
⎟
⎠
kapp.2
RT
[X12]
L3 ⋅ min .
mol3
K13
=
,
,
[X ] [HCl] −[X ]
(
)
1
0
12
where [HCl]0 is the amount of hydrogen chloride
released during the decomposition of Pd(PPh3)2Cl2
via reaction (1).
k
HCO
where kapp.1
=
k
=
is
P
ol TsOH CH OH ,
CO [ ][
][
]
3
app.2
k
HCO
and
CMP ol TsOH CH OH ,
CO [ ][ ][
]
НСО
3
Consequently,
Henry’s constant for CO solubility in toluene.
K13[X1][HCl]0
Rate equation (17) allows for quantitative substanꢀ
tiation of the observed dependences of the reaction
rate on the CO pressure and the methanol concentraꢀ
tion. Thus, in a singleꢀfactor experiment on РСО this
equation reduces to
(16)
[X12] =
.
1 + K13[X1]
An analysis of Eq. (16) shows that the second term
in its denominator can be neglected. Apparently, reacꢀ
tion (14) should be characterized by slight exotherꢀ
micity and a decrease in entropy; thus, the value of K13
must be less than 1. At the same time, [Х1] cannot be
greater than the initial catalyst concentration, which
PCO
kapp.3
HCO
(18)
r =
,
PC2O
HC2 O
A3 + b
was
1
×
10–3 to 1.5
×
10–2 mol/L. Owing to these conꢀ
13[X1] holds and Eq. (16)
ditions, the inequality
1
K
ӷ
where A3 = 1 +
kapp.3 kCМ[ol][TsOH][CH3OH], and HСО is Henry’s
a e ,
[CH3OH]2 + [PPh3]2 + fCМ
takes the compact form [X12] =
allowance for the relation [HCl]0 = 2CM, the equation
in this form appears as [X12] = 2 13[X1]CM
K13[X1][HCl]0. With
=
constant for CO.
K
.
Further transformation of Eq. (18) leads to the folꢀ
lowing expression:
The kinetic analysis of the data reported in [5]
showed that the contribution of complexes Х8 and Х9
to the overall balance of catalytic forms is negligible.
The application of the quasiꢀsteadyꢀstate approximaꢀ
tion to the given mechanism with allowance for this
fact and the above speculations about the concentraꢀ
tion of the intermediate Х12 result in the following rate
equation:
PCO A3HCO
b
(19)
=
+
PC2O.
r
kapp.3
kapp.3HCO
Representation of these relationships between r0
and РСО (Fig. 1) in the coordinates of Eq. (19) leads to
linear relations (Fig. 3). Their least squares treatment
led to the values for the parameters of the equation as
shown in the table.
In turn, the temperature dependence of the term
kC [CO] ol TsOH CH OH
[ ][
][
]
M
3
(17)
,
r =
2
2
1 + a CH OH + b[CO]2 + e PPh + fCM
A3HCO
[
]
[
]
is characterized by spread of data, indicating a
3
3
kapp.3
large uncertainty of determination of this parameter
by extrapolation. At the same time, the data on
where СМ is the total concentration of all forms of the
catalyst, M = X0 + X1 + X2 + X3 +… + X12, which is
equal to the initial concentration of Pd(PPh3)2Cl2; [ol]
C
b
are satisfactorily described by the Arrhenius
k
app.3HCO
K1K11
is the concentration of cyclohexene;
a
=
b =
,
equation:
1 + K1
b
K1K12
K1K8
2K1K13
1 + K1
K1K2K3K4K5K6
e
=
f
=
K =
,
,
,
,
kapp.3HCO
1 + K1
1 + K1
k7K.
1 + K1
and
k
=
146 1kJ mol
= 10−14.8 exp
,
.
L ⋅ min
Pa · mol
⎛
⎜
⎞
⎟
⎠
⎝
RT
The linearization of reaction rate equation (17) in
the singleꢀfactor experiment for Pd(PPh3)2Cl2 and
PPh3 in [5] led to the following expressions for the
parameters of the linearized forms:
In a singleꢀfactor experiment on the effect of methꢀ
anol concentration on the reaction rate, rate equation
(17) reduces to:
kapp.4 CH OH
[
]
70 3 kJ mol
f
3
= 10−6.70 exp
,
L·min.
mol
⎛
⎜
⎝
⎞
⎟
⎠
(20)
r =
,
2
kapp.1
RT
A + a CH OH
4 3
[
]
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KINETIC ASPECTS OF THE EFFECT OF CO PRESSURE
43
PC2O
HC2 O
РСО
· 10–10
,
L · min
mol
Pa ·
2
where A4
=
and kapp.4 =
+ e PPh + fCM,
1 + b
[
]
3
r0
4
3
2
1
PCO
kCM
ol TsOH .
[ ][
]
1
HCO
Further transformation of Eq. (20) leads to the folꢀ
lowing expression:
[CH3OH]
A4
[CH3OH]2.
a
(21)
=
+
2
3
r
kapp.4 kapp.4
The least squares processing of the data for Eq. (21)
A4
has shown that the parameter
kэф.4
nificant. Then this equation appears as
is statistically insigꢀ
4
5
[CH3OH]
a
kapp.4
(22)
=
[CH3OH]2.
0
10
20
30
40
r
Р2СО · 10–12, Pa2
[CH3OH]
The plots of
versus [CH3OH]2 in Fig. 4
Fig. 3. Fitting of the experimental data to Eq. (19). Conꢀ
centrations, mol/L: [C H ] = 0.1, [CH OH] = 0.45,
r0
show good agreement between the calculated (solid
line) and experimental (symbols) data. The statistical
6
10
3
–3
–3
[Pd(PPh ) Cl ] = 2.0
×
10 , [PPh ] = 8.0
×
10
,
3 2
2
3
–2
[TsOH] = 2.4
×
10 . Temperatures, K (
) 388.
1
) 368, (
2
) 373, (
3
)
A4
378, ( ) 383, and (
4
5
insignificance of the parameter
is supported by
kapp.4
the fact that these curves pass through the origin. The
the active forms of the catalyst from the catalytic cycle
to be estimated. So, from Eqs. (16), (17), and (19), it
follows that
a
data are satisfactorily described by the Arrhenius
kapp.4
law:
ΔHb k
= ΔH12 − ΔHH − E7 − ΔH2 − ΔH3
− ΔH4 − ΔH5 − ΔH6
app.3
75 1kJ mol
= 10−6.88 exp
,
a
(24)
⎛
⎜
⎝
⎞
⎟
⎠
kapp.4
RT
(23)
L2 ⋅ min.
ΔH
= ΔH11 + ΔHH − E7 − ΔH2 − ΔH
a kapp.4
3(25)
.
and
mol2
− ΔH4 − ΔH5 − ΔH6.
Note that we verified earlier the adequacy of this
kinetic model for a temperature of 378 K [14].
As
Δ
HH
=
⎯
6 kJ/mol [15], then
Analysis of the apparent activation energies allows
the ratios between enthalpies of ligandꢀexchange reacꢀ
tions (9), (12), and (13) responsible for the removal of
ΔH12 − ΔH11 = ΔHb k − ΔHa k + 2ΔHH
app.3
app.4
(26)
,
= −146 − (−75) + 2 ⋅(−6)= −83 kJ
Apparent constants of Eqs. (19) and (22)
T
, K
358
–
363
–
368
373
378
383
388
_
A3H
CO 10
kapp.3
10
Pa L min
,
0.14 0.03 0.10 0.04 0.08 0.02 0.13 0.01 0.12 0.01
mol
104,
b
L min
Pa mol
–
–
9.1 0.1
4.9 0.2
2.9 0.1 1.32 0.07 0.80 0.05
k
app.3HCO
L2 min
mol2
_
3
a
10.0 0.1 7.68 0.06 5.42 0.08 3.66 0.05 2.74 0.04
–
–
10
,
kapp.4
PETROLEUM CHEMISTRY Vol. 53
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44
AVER’YANOV et al.
[CH3OH]
r0
10
ΔH11 − ΔH13 = ΔHa k − ΔH f
kapp.1
app.4
· 10–3, min
(28)
= −75 − (−70) = −5 kJ.
Correspondingly,
1
2
3
ΔHe k
= ΔH8 + ΔHH − E7 − ΔH2 − ΔH3
− ΔH4 − ΔH5 − ΔH6,
app.2
8
6
4
2
(29)
(30)
ΔH12 − ΔH8 = ΔHb k − ΔHe k
app.3
app.2
+ 2ΔH
= −146 − (−143) + 2 ⋅(−6) = −15kJ.
H
These data can be converted using as a standard
one of the compounds involved in the ligand
exchange, for example, Pd(PPh3)2(CH3OH)2
:
4
5
Pd(PPh3)2(CH3OH)2 + 2CO
Pd(PPh3)2(CO)2 + 2CH3OH,
(31)
where
with Eq. (26);
Δ
H1
=
Δ
H12
– ΔH11 = –83 kJ in accordance
0
0.2
0.4
0.6
0.8
[CH3OH]2, mol2/L2
Pd(PPh3)2(CH3OH)2 + 2PPh3
Pd(PPh3)4 + 2CH3OH,
(32)
Fig. 4. Fitting of the experimental data to Eq. (22).
Р
=
СО
6
2.1
× 10 Pa; concentrations, mol/L: [C H ] = 0.1,
6 10
–3
–3
[Pd(PPh ) Cl ] = 2.0
×
10 , [PPh ] = 8.0 × 10 ,
3
3 2
2
for which the enthalpy is defined as
–2
–2
[TsOH] = 2.4
peratures, K: (
×
1
10 , and [
o
ꢀxylene] = 5.0
×
10 ; Temꢀ
) 378.
) 358, ( ) 363, (
2
3
) 368, ( ) 373, and (5
4
ΔH2 = ΔHe k − ΔHa k
= ΔH8 − ΔH11
app.4
app.2
(33)
(34)
= −143 − (−75) = −68 kJ.
Pd(PPh3)2(CH3OH)2 + HCl + 2Sol
HSol[Pd(PPh3)2(Cl)Sol] + 2CH3OH,
Similarly, using the previously calculated [5] values
for the apparent activation energy of the parameters
70 3kJ mol
f
10−6.70 exp
,
L· min
mol
⎛
⎜
⎝
⎞
⎟
⎠
=
and
RT
kapp.1
for which
Δ
H3 is defined by the equation:
3
.
143 7kJ mol
L min
−14.84
e
⎛
⎜
⎞
⎟
⎠
=
, we get
10
exp
,
ΔH3 = ΔH f
− ΔHa k = ΔH13 − ΔH11
kapp.1
app.4
(35)
⎝
RT
kapp.2
mol3
= −70 − (−75) = 5 kJ.
Relationships (26), (33), and (35) actually reflect
the stability series of the complexes
ΔH f
= ΔH13 + ΔHH − E7 − ΔH2 − ΔH3
− ΔH4 − ΔH5 − ΔH6,
kapp.1
(27)
ꢀ
ᮎ
Pd(PPh ) (CO) > Pd(PPh ) > Pd(PPh ) (CH OH) > HSol[Pd(PPh ) (Cl)(Sol)] ,
3
2
3
3
3
3
2
4
2
2
2
which differs from the one obtained on the basis of cific solvation of the coordinated carbonyl groups by
data on hydrocarbalkoxylation of cyclohexene with methanol [16]. Thus, the higher stability of the
cyclohexanol [4]:
Pd(PPh3)2(CO)2 complex in the presence of methanol
must inevitably lead to a reduction in its enthalpy of
formation in comparison with the Pd(PPh3)4 comꢀ
plex, which does not contain carbonyl ligands.
Pd(PPh3)4 > Pd(PPh3)2(CO)2
> Pd(PPh3)2(C6H11OH)2
The reported study was partially supported by
RFBR, research project No. 12ꢀ08ꢀ31280ꢀmol_a.
regarding the inversion of the formation enthalpies of
the complexes Pd(PPh3)4 and Pd(PPh3)2(CO)2. In this
context, it should be recognized that the enhancement
of the donor–acceptor properties of the ligands in the
order C6H11OH < CH3OH < Cl < PPh3 is not the only
factor responsible for the stability of palladium comꢀ
plexes in solution. Apparently, the solvation factor
should make additional contribution to the stabilizaꢀ
tion of these complexes. Then the stabilization of the
Pd(PPh3)2(CO)2 complex can be enhanced on passing
from cyclohexanol to methanol owing to stronger speꢀ
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