Journal of Organometallic Chemistry 842 (2017) 9e20

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Journal of Organometallic Chemistry

journal homepage: www.elsevier.com/locate/jorganchem

Kinetics and mechanistic study on deoxygenation of pyridine oxide

catalyzed by {MeReVO(pdt)} 2 dimer
Abdellatif Ibdah*, Salwa Alduwikat
Department of Chemistry, Jordan University of Science and Technology, Irbid, Jordan

a r t i c l e i n f o a b s t r a c t

Article history: The oxorhenium(V) dimer {MeReO(pdt)}2 (where pdt ¼ 1,2-propanedithiolate) catalyze the oxygen atom
Received 27 February 2017 transfer (OAT) reaction from the pyridine oxide to triphenylarsine (Ph3As). The rate law is given by n ¼ k
Received in revised form [Re-dimer][PyNO] and zero order dependence on Ph3As. The value of k at 25  C in CHCl3 is
26 April 2017
139 ± 3 L mol1 s1. The activation parameters are DHz ¼ 12.2 ± 1.0 kcal mol1 and
Accepted 28 April 2017
Available online 3 May 2017
DSz ¼ 7.9 ± 3.24 cal K1 mol1. According to the proposed mechanism, the rate determining step is the
oxidation of ReVO to ReVIIO2 and the pyridine release. The triphenylarsine enters the catalytic cycle after
the rate determining step. The reaction constant r ¼ 1.4 obtained from Hammett correlation with s for
Keywords:
Oxygen atom transfer
different substituted pyridine N-oxide. The computational study indicates that the oxidation of ReV to
DFT ReVII and release of the pyridine step is insensitive to the nature of the substituent on the pyridine with
Kinetics the average estimated activation barrier z11.5 kcal/mol from six different substituted pyridine oxide. It is
proposed that electron donor substituent enrich the equilibrium of the first step of the proposed
mechanism which is the coordination of the pyridine oxide with one rhenium atom to form I1 (Scheme
2). The electron donor substituent on the pyridine increase the concentration of I1 which will increase
the rate of the reaction as the n ¼ k2[I1].
© 2017 Elsevier B.V. All rights reserved.

1. Introduction The mechanistic studies of oxygen atom transfer catalyzed by

transition metal complexes have been studied as an essential step
Since decades, the oxygen atom transfer reaction (OAT) cata- in preparing a more efficient catalysis. In addition to experiments,
lyzed by high valent oxo transition metal complexes have been several computational studies have been employed into the high
attracted the scientific attention due to its application in biology [1] valent transition metal oxo complexes [6,8,10,11]. The proposed
and chemistry [2e4]. In biology, molybdenum and tungsten are catalytic cycle begins with oxidation of Mn¼O by an oxygen donor
exist in the active-site of certain enzymes. These enzymes catalyze to produce Mnþ2O2 followed by reduction of Mnþ2O2 back to Mn¼O
the oxygen atom transfer reaction and often called oxotransferase by an oxygen acceptor [1,4,5]. The ReV¼O/ReVIIO2 system can be
enzyme. Their catalytic cycle runs between M(VI)O2 and M(IV) ¼ O constructed to be used as catalysis for oxygen atom transfer. Several
(M ¼ Mo, W) [1] In chemistry, alkene oxidation, sulfide oxidation to dithiolate ReV¼O complexes has been prepared and their catalytic
sulfoxide, and deoxygenation of pyridine oxide through OAT re- activity has been examined [9,12e26]. The high valent rhenium(V)
actions are extensively employed in a wide range of areas of pre- oxo complexes have shown a great ability to catalyze the oxidation
parative organic chemistry. Considering the interest in developing reaction [16,20e28].
an efficient catalysis for oxygen atom transfer reaction (OAT), The deoxygenation of heteroaromatic N-oxides are important as
several transition metal complexes have synthesized and their intermediate step in the heterocycles synthesis [29,30]. Many of the
catalytic activity have been examined. Most of these complexes known methods for deprotection of pyridines are limited by the
have metal oxo (M ¼ O) bond in their structures like molybdenum, side reactions or by reduction of the ring substituents. Moreover,
tungsten [4,5], iron [2], manganese [6,7], and rhenium [8,9]. pyridine and other heteroarene N-oxides are important class of
heteroaromatic compounds in medicinal [31] and material chem-
istry [32]. The development of an efficient deoxygenation method
is highly desirable that can be used during the functionalization of
* Corresponding author. N-heterocycles [33,34].
E-mail address: aaibdah@just.edu.jo (A. Ibdah).

http://dx.doi.org/10.1016/j.jorganchem.2017.04.034
0022-328X/© 2017 Elsevier B.V. All rights reserved.
10 A. Ibdah, S. Alduwikat / Journal of Organometallic Chemistry 842 (2017) 9e20

The purpose of this work is to study the pyridine oxide deoxy- implemented in GAMESS [39,40]. All the structures were fully
genation catalyzed by oxorhenium dimer {MeReO(pdt)}2 (1) optimized with B3LYP using PCM solvation model of chloroform
(pdt ¼ 1,3-propanedithiolate) according to the following equa- with the following basis set: the LANL2DZ ECP augmented with 2f
tion. The dimeric catalyst was chosen because, in earlier studies, polarization functions for Re [41]and 6-31G(d) basis sets were used
dimeric systems had proved to be approximately 100 times more for other atoms. The structures were confirmed as minima or
effective than monomeric analogues [35]. transition states by calculating vibrational frequencies at same level

(1)

The above reaction is very important reaction to study because of theory and basis sets. The zero point, entropy change (DS ), and
no uncatalyzed reaction has been observed even though it's ther- the temperature correction to the energy is calculated with same
modynamically favored. The As-O (102.6 kcal/mol [36]) bond basis set and level of theory. Energies were refined with single
dissociation energy is stronger than the bond dissociation energy of point calculations on the optimized geometries using Minnesota
N-O (61.7 kcal/mol [37]) and the entropy change (DS z 0) is ex- exchange-correlation M11-L [42] with PCM solvation model of
pected to be very small. So, the above reaction has a negative Gibbs chloroform with the following basis sets: G3Large for As, 6-311(3df)
free energy (DG < 0). for S and Cl, 6-311G(d) for O, N, C and H, along with the same basis
set for Re.
2. Experimental section
3. Result and discussion
2.1. Reagent
The characterization of the product has been done with Ph3P
The Rhenium dimer {MeReO(pdt)}2 (1) (pdt ¼ 1,2-
using the 31P-NMR. The Ph3P is used only for the purpose of the
propanedithiolate) was synthesized according to the literature
product characterization because the dimer reacts with phosphine
experimental procedure [38]. Other reagents were purchased from
to form a monomer (Scheme 1) and phosphine monomer is very
commercial sources and used without extra purification. The sol-
slow comparing to dimer [35,43,44]. The catalysis 1 is stable with
vent used for kinetics study is chloroform. Bruker 400 MHz spec-
respect to monomerization by arsines, even over long reaction time
trometers used to obtain 1H and 31P NMR spectra. Benzene-d6 was
no MeReO(pdt) (AsPh3) monomer has not been detected. Also, the
used for rhenium(V) dimer 1H -NMR characterization to compare
catalysis 1 is found to be stable toward monomerization with pyr-
with literature values.
idine (the reaction product). This result is very important because
similar rhenium dimer can be monomerized with pyridine and
2.2. Kinetic measurements other N-heterocycles aromatic compounds (Scheme 2)
[23,28,44e47].
The reactions were studied at 25  C. Shimadzu scanning spec-
trophotometers (UV-2550) were used to record UVeVis spectra and
kinetic curves in cells with 1 cm optical path lengths. The reaction
progress was monitored from the intensity of pyridine oxide,
picoline oxide, and nitro pyridine oxide absorbance at, 307 nm,
309 nm, and 375 nm respectively. The time-absorbance data were
fitted to first-order kinetics, Eq (2), in which Y ¼ absorbance of
pyridine oxide substrate.

Yt ¼ Y∞ þ ðY0  Y∞ Þekobs t (2)

2.3. Computational methods

Computations were carried out using the DFT calculation, as Scheme 1. Monomerization reaction of {MeReO(pdt)}2 dimer occurs with phosphines.
 A. Ibdah, S. Alduwikat / Journal of Organometallic Chemistry 842 (2017) 9e20 11

Scheme 2. Monomerization reaction between dimer and N-heterocycles aromatic compounds.

Fig. 2. The pyridine oxide absorbance at 307 nm decrease with 0.5 mM pyridine oxide,
10.0 mM Ph3As, and 0.01 mM catalysis.

Based on the experimental observation the rate law can be

written as: R ¼ k[PyNO][Re][Ph3As]0. k ¼ 139 ± 3 M1s1. The first
order dependence on the pyridine oxide and the rhenium catalyst
imply that the rate determining step involve the pyridine oxide and
the catalyst only. The zero order dependence on the Ph3As indicates
that it inter the catalytic cycle after the rate determining step.

Fig. 1. 31P-NMR spectrum before (below) and after (above) completion (2.5 h) of a
reaction between 25 mM pyridine N-oxide, 140 mM PPh3, and 3.86 mM Re dimer. The 3.1. Para-substituted pyridine-oxide
resonance at 31.9 ppm in CDCl3 is for Ph3PO.

More kinetic measurements have been done with substituted

pyridine oxide to compare with the pyridine oxide. The 4-
nitropyridine oxide and picoline oxide (4-methyl-pyridine oxide)
The Ph3PO was the only oxide product formed from the deox- were the chosen substrates for the kinetic study. The absorbance
ygenation reaction of pyridine oxide (Fig. 1). The rest of the kinetics decrease of the nitro-pyridine oxide and picoline oxide were
measurement were made with Ph3As as oxygen acceptor. The observed under pseudo first order conditions of Ph3As ([Ph3As] »
absorbance decrease of pyridine oxide was monitored under [nitropyridine oxide] and [Ph3As] » [picoline oxide]) (Fig. 4). Similar
pseudo first order condition of Ph3As ([Ph3As] » [PyNO]) (Fig. 2). to PyNO reaction, the absorbance decrease confirmed a first order
The absorbance decrease conformed first order dependence on the dependence on the 4-nitropyridine oxide and picoline oxide but
pyridine oxide concentration. The k(obs) values obtained from the the nitro substituent is slower the pyridine oxide and the methyl
first order fitting of Eq (2) conformed zero dependent with respect substituent is faster than the pyridine oxide (Fig. 4).
to the Ph3As concentration (Fig. 3) and has linear dependence on The calculated k(obs) values from the first order fitting confirmed
the rhenium dimer catalyst concentration confirming the first order the zero order dependence on the Ph3As and first order depen-
dependence on rhenium dimer (Fig. 3). dence on the rhenium catalyst for both 4-nitropyridine oxide and
Fig. 3. (Left) Plot of k(obs) against the Re concentration with 0.5 mM Pyridine oxide and 10.0 mM Ph3As. (Right) Plot of kobs against Ph3As concentration with 0.5 mM pyridine oxide
and 0.01 mM of Re catalyst.

Fig. 4. (Left) The picoline oxide absorbance at 309 nm decrease with 0.38 mM picoline oxide, 10.0 mM Ph3As, and 0.01 mM catalysis. (Right) The 4-nitropyridine oxide absorbance
at 375 nm decrease with 0.25 mM 4-nitropyridine oxide, 5.0 mM Ph3As, and 0.05 mM catalysis.

picoline oxide (see supporting information). These kinetics results

are equivalent to the pyridine oxide results. Also, the first order
fitting on pyridine oxide substrates retain even at low concentra-
tion of Ph3As (less than the pseudo order conditions) which
confirm the zero dependence on the arsine. The rate constant k is
16.5 ± 0.8 M1s1 and 388 ± 14 M1s1 for 4-nitropyridine oxide
and picoline oxide, respectively.
The reaction rate became slower with electron withdrawing
substituent (NO2 substituent) on the pyridine oxide and faster with
electron donor substituent (methyl substituent). The rate deter-
mining step remains same and the Ph3As inter the catalytic cycle
after the rate determining step.

3.2. Reaction scheme and the mechanism

The kinetics data allow the construction of the reaction mech-

anism as presented in Scheme 3. The first step of the proposed
mechanism is the coordination of the pyridine oxide to one
rhenium atom concomitant with release one Re-S coordinate bond
to form five coordinated intermediate I1 in fast equilibrium. The Scheme 3. The Proposed mechanism of the oxygen atom transfer catalyzed by
following step is the irreversible release of the pyridine to form of {MeReVO(pdt)2 dimer.
 A. Ibdah, S. Alduwikat / Journal of Organometallic Chemistry 842 (2017) 9e20 13

catalyst will be restored to start another cycle. Analogous system of

rhenium catalysts adopt similar kinetics dependence that the
ReO(VII)
2 formation is the slow step followed by fast addition of the
oxygen acceptor (e.g Ph3P/Ph3As) [44,48,49].
On the basis of Scheme 3, the rate expression can be derived
considering prior-equilibrium in the first step (I1 formation) fol-
lowed by the R.D.S formation of I2 (Full derivation of the rate law is
in the supporting information).

k1 k2
v¼ ½1½PyNO (3)
k1
Eq (3) can be simplified to Eq (4).

v ¼ Keq K2 ½1½PyNO (4)

v ¼ K½1½PyNO; k ¼ Keq k2 (5)

3.3. Hammett analysis

Fig. 5. The Hammett analysis of the relative rate constant of pyridine oxide
substituent. The experimental second order rate constants are sensitive to
the nature of the substituent on pyridine oxide Me > H > NO2, with
reaction constant r ¼ 1.4 ± 0.1 (Fig. 5). The reaction constant is
Table 1
The ratio of the rate constant (kX/kH) to hammett substituent content. estimated from the relative rate constant to the hammett substit-
uent constant (Table 1). The second order rate constant (k) depends
X-PyN-O kX L mol1 s1 kX/kH s
on the Keq and k2 values (Eq (5)). The increase in the rate constant
NO2-PyN-O 15.3 0.11 0.78 can be traced to increase of either Keq or k2 or both. The electron
PyN-O 136.3 1.00 (rel) 0.0
donor substituent on pyridine oxide increases the rate of reaction.
Me-PyN-O 390.2 2.87 0.17
The first equilibrium of the proposed mechanism will be enhanced
with more electron donor substituent as more basic ligand will
ReO(VII)
2 intermediate I2 and it is the rate controlling step. The Ph3As coordinate faster. The second step (oxidation of rhenium and
react with the ReO(VII)
2 intermediate I2 in fast step to reduce ReVII reduction of pyridine oxide) is thought to be inhibited with electron
(V)
and form Re -OAsPh3 intermediate. Then the Re-S coordinate donor substituent on the pyridine oxide because reduction of the
bond will be regenerated concomitant to release Ph3AsO. The pyridine ring will be less favored by electron donor substituent. The

Scheme 4. The simplified reaction model for the DFT calculation.

Fig. 6. The DFT optimized structure: A is the Me(pdt)ReVIIO2, B is the optimized structure of Me(pdt)ReV-OPyN intermediate, C is the transition state structure of the pyridine release
and Me(pdt)ReVIIO2 formation.
 Fig. 7. The DFT calculated reaction coordinate of the simplified model reaction.

Table 2
The enthalpy, entropy, and Gibbs free energy of activation of the proposed slow step with different pyridine oxide substituent and the fast step.

Reaction DH z (kcal/mol) DS z cal K1 mol1 DG za (kcal/mol)

11.5 0.71 11.66
O O
S Me S Me
Re Re
S O S O
N N
NO 2 NO 2

O 11.3 0.167 11.28

O
S Me S Me
Re Re
S O S O
N N
Cl Cl
11.6 0.64 11.79
O O
S Me S Me
Re Re
S O S O
N N

O O 11.7 0.39 11.55

S Me S Me
Re Re
S O S O
N N
Me Me

O O 11.2 0.11 10.84

S Me S Me
Re Re
S O S O
N N
OMe OMe

O O 11.4 0.72 11.19

S Me S Me
Re Re
S O S O
N N
NMe 2 NMe 2

O O 6.1 44.1 19.2

S Me S Me
Me As
Re Re
S O O
S
AsMe 3

a
At T ¼ 298.15 K; DG z ¼ DH z - TDS z
 A. Ibdah, S. Alduwikat / Journal of Organometallic Chemistry 842 (2017) 9e20 15

experimental results shows the electron donor substituent in- rate determining step and the fast step of the reaction as well. Due
creases the reaction rate constant and the electron withdrawing to the time limitation to run the calculation on the actual catalysis
substituent decreases the reaction rate constant. This suggests that and the reactants, certain simplification has been used in which the
the first equilibrium is more affecting by nature of the substituent Me(pdt)ReVO-OPyN-X and Me(pdt)ReVIIO2 (Scheme 3) are used in
than the second oxidation step. place of I1 and I2 intermediates in Scheme 2 and Me3As is used in
place of Ph3As. This small model of the dimer is valid as the other
3.4. Computational study half of the Re dimer isn't directly involved in the proposed
mechanism.
To gain a better understanding on the reaction mechanism and In the kinetics experiments only three substrates have been
the substituent effect, the DFT calculations have been done on the used because of the starting materials availability. But in the

Table 3
Selected bond lengths (Å) and angles and Mulliken charges on Re, O, and N.

Re-O2 Re-O1 O1-N Re-O1-N angle Charge, Re Charge, O1 Charge, N

O 2 1.68 2.10 1.34 125.4 0.44 0.53 0.05

S Me
Re
S O1
N
NO2

O2 1.68 1.89 1.62 126.6 0.57 0.52 0.21

S Me
Re
1
S O
N
NO2

O2 1.68 2.08 1.36 123.9 0.44 0.54 0.07

S Me
Re
S O1
N
Cl

O2 1.68 1.89 1.64 126.2 0.57 0.52 0.23

S Me
Re
S O1
N
Cl

O 2 1.68 2.08 1.36 124.6 0.45 0.55 0.07

S Me
Re
S O1
N

O2 1.68 1.88 1.66 126.1 0.58 0.53 0.22

S Me
Re
1
S O
N

O2 1.68 2.07 1.36 123.5 0.45 0.55 0.07

S Me
Re
1
S O
N

O2 1.68 1.88 1.66 126.3 0.58 0.53 0.23

S Me
Re
1
S O
N

O2 1.68 2.06 1.37 124.3 0.46 0.55 0.09

S Me
Re
S O1
N O

O2
1.68 1.87 1.67 126.3 0.58 0.52 0.25
S Me
Re
1
S O
N O

O 2 1.68 2.05 1.37 125.0 0.46 0.56 0.10

S Me
Re
S O1
N NMe2

O2
1.68 1.87 1.68 126.6 0.59 0.53 0.26
S Me
Re
1
S O
N NMe2

O 1 1.69 1.69 0.65 0.46

S Me
Re
S O2
16 A. Ibdah, S. Alduwikat / Journal of Organometallic Chemistry 842 (2017) 9e20

computational study, more substrates were tested to understand mulliken charges on Re increases as results of the oxidation and
the substituents effect (Scheme 4). Six substituted pyridine oxide the negative charges on the N increases as result from the
have been used varying from strong electron withdrawing to strong reduction. The charges on the nitrogen doesn't change with sub-
electron donor substituent. stituent even though there are a little increase on the charge with
The calculated structure of ReVIIO2 key intermediate is a dis- strong electron donor substituent (MeO-, Me2N-). There is small
torted trigonal bipyramid in which the oxo group occupy the elongation observed on the N-O with MeO- and Me2N- substitu-
equatorial position (Fig. 6, A). This result is consistent with earlier ent compared to others in both transition state and intermediates.
computational studies that showed the dioxo d0 octahedral com- The Re-O1 are not changed significantly with substituents for both
plexes form stable cis-dioxo complexes [50,51]. The optimized optimized minima and transition state. The substituents on the
structure of Me(pdt)ReVO-OPyN and its transition state structure of pyridine oxide don't have any significant changes on the N-O and
pyridine release are illustrated in Fig. 7 (B and C). The other opti- Re-O1 bond length and the charges on both N and O1 which
mized structure and transition state structure of the substituted confirm that the rate determining step is not sensitive to the na-
pyridine oxide are presented in the supporting information along ture of the substituent.
with the coordinates. All the transition states have been verified by The DFT estimated the thermodynamic parameters of the slow
the intrinsic reaction coordinate (IRC) calculation on the located oxidation ReV to ReVII and release of the pyridine step is exothermic
transition state. and exergonic for all substituted pyridine oxide (Table 4). But more
The activation barrier for ReVIIO2 formation and pyridine negative DH and DG obtained with electron withdrawing group
release were calculated for six pyridine oxide substituents because the reduction of N of the aromatic ring will be more
(Table 2). The calculated barrier (DH z) is unaffected by the nature favored with electron withdrawing group.
of the substituent on the pyridine oxide and The computational results explain the zero order dependence
approximately z 11.5 kcal/mol. The average Gibbs free energy of on the triphenylarsine but doesn't explain the Hammett depen-
activation (DG z) is 11.4 kcal/mol and also not affected by the dence. The Hammett analysis shows that the electron donating
nature of the substituent. The entropy of activations (DS z) of the substituent increase the rate of the reaction. Based on computa-
slow step are very small and slightly positive except for NO2 and H tional results, it can be assume that the Hammett substituent effect
substituent are slightly negative. The activation barrier of the fast came from the first equilibrium step. As basicity of pyridine oxide
step (nucleophilic addition of the Me3As to ReVIIO2 step) is increases with electron donor substituent, the first equilibrium step
6.15 kcal/mol (Table 2) and has large negative entropy of activa- will shift to right to form more I1 (Scheme 2) which will increase
tion which agree with associative nature of the reaction. The the reaction rate.
activation barrier is lower than the activation barrier of the rate The influence of the substituent on the first equilibrium is not
determining step which agree with the experimental finding that applicable to study computationally because of large time needed
the arsine inter the catalytic after the rate determining step. The to run the calculation on the dimer without simplification. But it
reaction coordinate has been calculated by DFT for the proposed can be examined indirectly relative to pyridine according to Eq (3).
slow and the fast steps of the mechanism using the above reaction The DH of Eq (3) indicate how the substituent can influence the first
model (Fig. 7). equilibrium step compare to pyridine oxide. Since the other
The above results of DH z promoted us to examine the Re¼O, rhenium atoms isn't involve in the reaction, it can be studied using
Re-O, and N-O bond length of the ReV intermediates and the a small model of the rhenium dimer (Eq (4)). Eq (4) is an isodesmic
transition states in addition to mulliken charges on ReV, O, N, and reaction in which the error of the computation will be the mini-
ReVII. Table 3 summarize our results. In all transition states the Re- mum. Table 5 summarized our results.
O length decreases and the O-N bond increases as expected. The

O O
S Me S Me
Re Re
S O S O
S + S (3)
Me Re R N+ O- Me Re + H N+ O-
S S
O O
N N

H R

R
O O
S S
Me Re + R +
N O - Me Re + H N+ O- (4)
S S
O O
N N

H R
 A. Ibdah, S. Alduwikat / Journal of Organometallic Chemistry 842 (2017) 9e20 17

Table 4
The enthalpy, entropy, and the Gibbs free energy of the proposed slow step with different pyridine oxide substituent and the fast step.

Reaction DH (kcal/mol) DS cal K1 mol1 DG a (kcal/mol)

O O 21.7 46.6 35.6
S Me S Me
Re Re N NO2
S O S O
N
NO2

O O 19.9 45.9 33.6

S Me S Me
Re Re N Cl
S O S O
N
Cl

O O 17.7 44.1 30.8

S Me S Me
Re Re N
S O S O
N

O O 16.8 46.9 30.8

S Me S Me
Re Re N Me
S O S O
N
Me

O O 17.7 47.7 31.9

S Me S Me
Re Re N OMe
S O S O
N
OMe

O O 14.6 46.8 28.6

S Me S Me
Re Re N NMe2
S O S O
N
NMe2

O O 17.5 44.8 4.1

S Me S Me
Me3As
Re Re
S O S O

AsMe3

a
At T ¼ 298.15 K; DG ¼ DH - TDS .

Table 5
The enthalpy and Gibbs free energy of reaction 4 with different substituent.

Reaction DH4 kcal/mol DS4 cal K1 mol1 DG4 a kcal/mol

O O 3.80 2.72 4.61
S S
Me Re + ON
2 N+ O- Me Re + H N+ O-
S S
O O
N N

H O2N

O
S
O
S
0.16 1.81 0.70
Me Re + Cl N+ O- Me Re + H N+ O-
S S
O O
N N

H Cl

O
S
O 0.00 0.00 0.00
S
Me Re + H N+ O- Me Re + H N+ O-
S S
O O
N N

H H

O O 1.73 1.69 1.22

S S
Me Re + N+ O- Me Re + H N+ O-
S S
O O
N N

O O 2.58 3.39 1.57

S S
Me Re + MeO N+ O- Me Re + H N+ O-
S S
O O
N N

H MeO

O O 5.71 6.95 3.64

S S
Me Re + Me2N N+ O- Me Re + H N+ O-
S S
O O
N N

H Me2N

a
At T ¼ 298.15 K; DG ¼ DH - TDS .
18 A. Ibdah, S. Alduwikat / Journal of Organometallic Chemistry 842 (2017) 9e20

Fig. 8. (Left) Plot of enthalpy of Eq (4) (DH4 ) against Hammett (s) substituent constant, (Right) Plot of DG4 of Eq (4) against Hammett (s) substituent.

The enthalpy (DH4 ) and Gibbs free energy (DG4 ) of reaction 4 energy of Eq (4) (DG4 ) values with the Hammett (s) substituent
provides a qualitative analysis how the coordination to rhenium constant (Fig. 8).
center is influenced by the nature of the substituent on the pyridine
oxide. The negative enthalpy and Gibbs free energy of reaction with
3.5. Activation parameters
electron donor substituent (entries 1 and 2) indicates that the
rhenium coordinate better with electron donor substituted pyri-
The second-order rate constant for the pyridine oxide reaction,
dine oxide and prefer the electron donor substituent compare to
as defined in Eq (1), was determined at the different temperatures
pyridine oxide. This will shift the equilibrium (Keq) to right to form
of 15.0, 20.0, 25.0, and 35.0  C. The data were fit by the transition-
more I1 intermediate (Scheme 2). The positive enthalpy and Gibbs
state theory equation
free energy of reaction with electron withdrawing substituent
(entries 4, 5 and, 6) indicate that rhenium center coordinate weaker  
lnðk=TÞ ¼ lnðkB =hÞ þ DSz R  DHz RT (6)
with electron withdrawing substitute. This will shift the equilib-
rium (Keq) of the proposed mechanism to the left to form less I1 Fig. 9 displays the plot of ln(k/T) vs 1/T for pyridine oxide. The
intermediate. These results agree with experimental finding that plots of nitro and methyl substituent are available in supporting
NO2 substituent is slower than pyridine oxide and the methyl information. From slope and the intercept the DHz in kcal mol1
substituent is faster than pyridine oxide. Also, there is a good cor- and DSz cal K1 mol1 were obtained. Table 6 summarize our
relation between the enthalpy of Eq (4) (DH4 ) and Gibbs free results.
The experimental entropy of activation DSz ¼ DS1 þ DS2 z. The

DS1 is substantially negative because two molecules associate to
one molecules in the first equilibrium. The DSz2 (estimated in
Table 2) are slightly positive for NO2 and H substituent and slightly
negative methyl substituent. The experimental DSz for the three
pyridine oxide substrates are negative means that DS+1 is the most
anticipating in the total entropy of activation.
The experimental DHz increases as electron withdrawing sub-
stituent attached to pyridine oxide (DHzNO2 > DHzH > DHzMe). These
results agree with experimental reaction rate that the picoline N-
oxide is faster than pyridine N-oxide and pyridine N-oxide is faster
than 4-nitropyridine N-oxide. The experimental
DHz ¼ DH1 þ DH2 z. The DFT estimated values DHz2 are 11.7, 11.6,
and 11.5 kcal/mol for 4-picoline N-oxide, pyridine N-oxide, and 4-
nitropyridine N-oxide, respectively (Table 2). The projected values
of DH+1 (DH+1 ¼ DHz(exp) - DHz2(DFT)) are 2.7, 0.5, and 1.2 kcal/mol,
respectively. The DH+1 shows how the thermodynamic of the first
equilibrium changed by the nature of the substituent. It is less

Table 6
The estimated activation parameters of reaction 1

substrate DHz/(kcal/mol) DSz (cal/mol.k)

4-nitropyridine N-oxide 14.3 ± 1.0 10 ± 3
pyridine N-oxide 12.2 ± 1.0 8 ± 4
Fig. 9. Plot of ln(k/T) versus 1/T of the pyridine oxide (0.5 mM) reaction with triphenyl
4-picoline N-oxide 10.5 ± 0.2 11 ± 1
arsine (1 mM), and rhenium dimer (0.014 mM).
 A. Ibdah, S. Alduwikat / Journal of Organometallic Chemistry 842 (2017) 9e20 19

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dx.doi.org/10.1016/j.jorganchem.2017.04.034. Adv. Inorg. Chem. 54 (2003) 157e202.
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