Kinetic analysis of the complete mechanochemical synthesis of a palladium(II) carbene complex

Article abstract of DOI:10.1016/j.inoche.2019.107622

Benzimidazoline-2-ylidene complexes of palladium(II) were synthesized mechanochemically in a vibratory ball mill. Complete syntheses began with preparation of benzimidiazolium halides from commercially available starting materials. These “greener chemistr

Full text of DOI:10.1016/j.inoche.2019.107622

Inorganic Chemistry Communications 111 (2020) 107622
Contents lists available at ScienceDirect
Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
Kinetic analysis of the complete mechanochemical synthesis of a palladium
(
II) carbene complex
⁎
Rachel J. Allenbaugh , Jonathon R. Zachary, A. Nicole Underwood, J. Dillion Bryson,
Joseph R. Williams, Angela Shaw
Department of Chemistry, Murray State University, 1201 Jesse D. Jones Hall, Murray, KY 42071, United States
G R A P H I C A L A B S T R A C T
A R T I C L E I N F O
A B S T R A C T
Keywords:
Benzimidazoline-2-ylidene complexes of palladium(II) were synthesized mechanochemically in a vibratory ball
mill. Complete syntheses began with preparation of benzimidiazolium halides from commercially available
starting materials. These “greener chemistry” syntheses proceed in high yield and require minimal purification
using environmentally benign solvents. Kinetic analysis shows that liquid assisted grinding impedes the pro-
duction to benzimidazolium halides while enhancing the production of the palladium-carbene complex.
Mechanochemistry
Ball mill
Solid state kinetics
Green synthesis
Palladium-carbene
1
. Introduction
Mechanochemical reactions involve the use of mechanical energy,
organometallic mechanosynthesis including (1) ligand exchange/func-
tionalization and/or co-crystallization of organometallic species pre-
pared by non-mechanochemical methods [6–11], (2) preparation of
carbonyl complexes, [11–12] and (3) formation of new metal-organic
ligand bonds [5,13–24], less than half involve mechanochemical C-H
bond activation [5,17–24]. This lack of total syntheses is a problem for
widespread adoption of mechanochemistry, as maintaining both solu-
tion and mechanochemical systems can be impractical.
often provided by grinding or shaking reagents, rather than thermal or
light energy to induce reactions, while using little or no solvent. Along
with a move to more environmentally benign solvents [1] when solvent
use cannot be avoided, mechanosynthesis can provide a less expensive,
greener alternative to solvent-based processes [2–3]; however, work on
the preparation of ligands as part of a total mechanosynthesis of or-
ganometallic complexes is limited [4–5]. Of the existing types of
Pd-C organometallic species utilized in Heck-type coupling reac-
tions [25–26] have been mechanosynthesized previously [5,20,22].
⁎
Corresponding author.
E-mail address: rallenbaugh@murraystate.edu (R.J. Allenbaugh).
https://doi.org/10.1016/j.inoche.2019.107622
Received 9 September 2019; Received in revised form 16 October 2019; Accepted 21 October 2019
Available online 25 November 2019
1387-7003/ © 2019 Elsevier B.V. All rights reserved.

R.J. Allenbaugh, et al.
Inorganic Chemistry Communications 111 (2020) 107622
Scheme 1. Mechanochemical synthesis of
2
3
b, 3b proceeds through intermediates (2a,
a). Isolation of 2b/3b and addition of
Na
2
CO
3
in each reaction is necessary to
maximize yields.
Palladium-imidazoline-2-ylidene complexes have been prepared by
mechanochemical transmetallation [24] and in a two-step method via
tetrachloropalladate imidazolium salts [27]. However, to the authors’
knowledge this is both the first solvent-free preparation to produce a
benzimidazoline-2-ylidene Pd-C bond directly and the first kinetic
analysis of such a total synthesis (Scheme 1).
Kinetic understanding of “molecular” mechanochemistry is also in
early development, as was first reviewed by Ma and coworkers in 2014
[
28]. Since then, work by our group [29–30] and others [31–34] has
focused on determining whether or not the models [35] originally de-
veloped for the synthesis of inorganic network materials (e.g. metal
oxides and nitrides) are applicable to molecular mechanochemistry.
Previous research by our group [29–30,36], has shown that the physical
properties of a mechanochemical reaction mixture can both aid and
retard reaction as those properties change with the reaction mixture
composition. Here the effects of liquid assisted grinding (LAG) with a
changing parameter are explored as the alkyl halide in the reaction
mixture acts as both a reagent and a modifier of the grinding en-
Fig. 1. Kinetic data for the synthesis of 2b (left) and 3b (right) using 2
equivalents (□), 3 equivalents (△) and 3 equivalents of RX under LAG con-
ditions (○). The results of JMAYK (solid lines) and FW modeling (dashed lines)
are shown.
likely caused by steric effects in the solid state not observed in solution
synthesis.
1
Using H NMR spectroscopy, the relative amounts of 1, 2a or 3a,
and 2b or 3b were used to determine the reaction coefficient, , which
corresponds to the fraction of complete conversion. Because of the high
volatility of the alkyl halides, each reaction mixture could be sampled
only once. At least three replicates were analyzed at each time interval,
and the average versus time data for various preparations of 2b and
3b are shown in Fig. 1.
vironment. The parameter, determined as a ratio of
of solid, is used to differentiate LAG reactions (0 <
slurrying methods (2 < < 12) and solution syntheses ( > 12)
37–38].
µ
L of liquid to mg
< 2) from
[
In-situ reaction monitoring via IR [39–40] or Raman [41–44]
spectroscopy or X-ray diffractometry [42,45–49] is ideal for mechan-
ochemical preparations; however, inexpensive, readily available ex-situ
methods are more likely to be of interest to those for whom mechan-
ochemistry is a cost-saving, low environmental impact means of pro-
ducing products. For that reason, this and previous work [29–30,36]
has focused on analysis of mechanochemically prepared compounds by
This kinetic analysis is somewhat unique because the synthesis of a
well-defined intermediate can be simultaneously tracked as shown in
Fig. 2. The relative amount of intermediate that builds up in the reac-
tion mixture relates directly to the amount of liquid, MeI or CDCl ,
3
present in the reaction mixture, implying that the intermediate may be
stabilized. However, the possibility that the increased
parameter
1
H NMR spectroscopy.
merely decreases the availability of intermediate and effectiveness of
the milling impacts cannot be discounted.
2
. Results and discussion
2.2. Benzimidazoline-2-ylidene complex preparation
2
.1. Benzimidazolium salt preparation
The literature preparation [25] of these complexes requires heating
Pd(OAc) and the desired benzimidazolium salt in DMSO. Presumably
2
Typical benzimidazolium halide preparation has two steps. The
due to the dilution and stabilization of the resulting acetic acid by-
product by the solvent, high yields are obtained. In the case of me-
chanochemical reaction, acetic acid does inhibit the reaction, but ad-
alkyl benzimidazole is prepared from benzimidazole before a second
equivalent of alkyl halide is added to prepare the salt [50–52]. Im-
proved single-step syntheses has involved use of a pressure tube and
large excesses of alkyl halide [53]. Mechanochemical syntheses of a
single benzimidazolium salt [17], N,N′-dipicolylbenzimidazolium bro-
dition of Na
2
CO
3
gives complete conversion. Initial experiments
focused on neat reaction as shown in Fig. 3; however, these reactions
did not near complete conversion in a reasonable timeframe. Both to-
mide, has been reported using NaHCO
3
as an aid to deprotonation.
luene-d
8
and CDCl
3
were tried as LAG solvents, but toluene-d
8
did not
Modifying that preparation to use Na
2
CO
3
gave rapid preparation of 2b
improve results over neat reactions. By adding CDCl
3
for a LAG
and 3b with higher conversion (Fig. 1). Details of the synthesis and
characterization are provided in the Supporting Information. NMR
sample preparation was simplified because no bubbling from the de-
composition of carbonic acid was observed. Na
2
CO proved such an
3
effective promoter of this reaction that high yields of 2b can be ob-
tained by simply mixing the reagents and allowing them to sit over-
night, if large excesses of methyl iodide are used. Mechanosynthesis
was not effective for all alkyl halides, however. Benzyl chloride and
butyl iodide were both unreactive with 1 under the reaction conditions,
and neither the desired products nor the alkyl-benzimidazole inter-
mediates were observed. This is consistent with the reduced reactivity
of benzyl chloride in comparison to benzyl bromide due to the stronger
C-X bond. The difference in the reactivities of methyl and butyl iodide is
Fig. 2. Kinetic data for the synthesis of intermediates 2a (left) and 3a (right)
using 2 equivalents of RX (□), 3 equivalents of RX (△) and 3 equivalents of RX
under LAG conditions (○).
2

R.J. Allenbaugh, et al.
Inorganic Chemistry Communications 111 (2020) 107622
Table 1
Results of kinetic modeling, where parameters are defined as in Eqs. (1)–(3).
Cond.
JMAYK
FW
ER
−
−
−
−
−
−
−
3
3
3
3
3
3
3
−4
2
3
2
b
b
c
3 MeI
neat
k = 5.644 × 10
k
1
= 1.028 × 10
= 3.562 × 10
= 0.9882
34.68
−
2
n = 5.904
k′
2
2
2
2
2
2
2
2
2
2
2
2
R
= 0.9951
R
−4
3
MeI
k = 2.981 × 10
k
1
= 5.225 × 10
= 1.020 × 10
= 0.9845
0.6354
−
2
LAG
n = 2.171
k′
2
2
R
= 0.9834
R
−5
2
MeI
k = 5.246 × 10
k
1
= 8.271 × 10
= 3.438 × 10
= 0.9912
−
2
neat
n = 5.366
k′
4.382
2
2
R
= 0.9939
R
−4
3 BnBr
neat
k = 4.305 × 10
k
1
= 1.530 × 10
0.8501
−
−
−
2
2
2
n = 3.705
k′
= 2.4078 × 10
= 0.9464
2
2
R
= 0.9445
R
−3
3
BnBr
k = 6.075 × 10
k
1
= 1.056 × 10
= 2.0962 × 10
= 0.9890
1.758
1.732
0.2438
LAG
n = 2.180
k′
2
2
R
= 0.9902
R
−5
2
BnBr
k = 4.226 × 10
k
1
= 7.160 × 10
= 2.7519 × 10
= 0.9801
Fig. 3. Kinetic data for the synthesis of 2c neat (
×
) and under LAG conditions
neat
n = 3.956
k′
2
2
with (○) and without (△) added KI. To check that repeated sampling did not
affect results, single sample trials were also carried out (□). The results of
JMAYK (solid lines), FW modeling (dashed lines), and FW modeling with
variables restricted to positive values (dotted lines) are shown.
R
= 0.9826
R
−3
neat
k = 2.186 × 10
k
1
= 6.113 × 10
= -8.3542 × 10
= 0.9905
−
3
n = 0.5221
k′
2
2
R
= 0.9887
R
−3
k
1
= 2.442 × 10
k′
= 0
2
R
= 0.7672
reaction, complete conversion could be reached in 630 min. As with the
LAG preparation of the benzimidazolium salts, deuterated LAG solvents
were utilized to simplify the NMR analysis by minimizing the appear-
ance of solvent signals. To check that sampling the reaction mixtures
multiple times was not changing the conversion, single-sample trials
were also performed at 180, 450, and 675 min. The analysis at 675 min
was repeated three times because on the first trial the ball became
stuck, leading to a reduced conversion. The two other trials both
reached complete conversion. This is the main difference between
sampling the reaction mixture at multiple time intervals and only once.
Any problems with bulk mixing due to a compaction of the reaction
mixture and the ball are avoided by manually checking the reaction
mixture.
−
3
−3
LAG
k = 4.837 × 10
n = 0.8147
k
1
= 6.330 × 10
1.278
−3
k′
= -3.593 × 10
= 0.9663
2
2
R
= 0.9673
R
−
3
k
1
= 4.612 × 10
= 0
k′
2
R
= 0.9521
'
k1 + k
2
= 1
'
'
(k1+k2)t
k2 + k1e
(2)
The models were evaluated for their fit to the data based on coef-
2
ficients of determination (R values); however, to compare the utility of
the two models to each other, evidence ratios (ER) were utilized.
Calculated from Akaike weights (w, which vary from 0 to 1 based on the
Mechanochemical preparation of the imidazoline-2-ylidene palla-
dium complex Pd(IBz)
2
Cl
2
from reaction of HIBzCl and K
2
2
PdCl
[PdCl
[PdCl
4
4
in the
], and
4
how strongly one model fits the data compared to others), ER ≥ 10
presence of KOH has been shown to initially form (HIBz)
−
4
show the JMAYK model is significantly better, while ER ≤ 10 show
that the FW model is better (Eq. (3)). These values for determining
significant ER were originally proposed by Finney and Finke [55]. More
information on the determination of w and ER is provided in the
Supporting Information and in previous work, as well as tables of all
calculated values [30]. The results of kinetic analysis show that both
models provide good fits to the data, and neither model is preferable
based on the ER values (Table 1).
the byproduct KCl must be removed before the (HIBz)
2
4
] can be
further ground to produce Pd(IBz)
2
Cl
2
[27]. Unlike that preparation,
either a one-pot or “shotgun” style reaction where reagents are added in
multiple steps will produce 2c; however, the reactions do not proceed
cleanly, and yields are low. This is attributed to the inhibition of the
desired reaction by excess iodine salt. Addition of KI in the LAG
synthesis of 2c inhibits reaction after the initial mixing period (Fig. 3).
PdI does not react with 2b under the conditions employed here.
2
w
JMAYK
ER =
w
FW
(3)
2.3. Kinetic analysis
Because the FW model has separate parameters for nucleation and
autocatalytic growth, it is the simpler model to use in examining the
effects of reaction parameters. In the synthesis of 2b and 3b, significant
amounts of the intermediates 2a and 3a build up in the reaction mix-
Based on the sigmoidal nature of the versus time curves (Fig. 1),
two different kinetic models were utilized to fit the data, the Johnson-
Mehl-Avrami-Yerofeev-Kolmogrov (JMAYK, Equation (1)) and Finke-
Watzky (FW, Eq. (2)) [54] models using the form of the JMAYK model
ture and reaction does occur in the absence of added Na
2
CO , so the
3
proposed by Finney and Finke [55]. In those equations, k, k
1
, and k′ are
2
rate limiting step would seem to involve the alkyl-benzimidazole spe-
cies. That increasing the amount of RX added does not significantly
alter the rate points to alkyl-benzimidazole based nucleation sites.
rate related parameters where k′
2
is dependent on initial concentration
according to k′ = k [A] , where t is time, and n is the Avrami ex-
2
2
0
ponent. Both models are based on a process of nucleation and auto-
catalytic growth. The JMAYK model is an empirical method, and Finney
and Finke [55] have pointed out that this model combines both nu-
cleation and growth under a single rate related parameter (k). Their
Using 2 equivalents of both MeI and Na
2
CO , the reaction begins as a
3
LAG process with an parameter of 0.38 based on the average volumes
and masses of reagents used for the kinetic studies (see Supporting
Information). Over the course of the reaction, this drops to zero and the
reaction mixture becomes a compacted, dry powder. Addition of an
extra equivalent of MeI modified the initial and final parameters to
0.56 and 0.10, respectively. The lack of significant changes to the ki-
netics of the reaction, means that LAG reactions cannot be thought of
model has separate rate related parameters k
1
and k
2
for nucleation and
autocatalytic growth.
n
=
1
e (kt)
(1)
3

R.J. Allenbaugh, et al.
Inorganic Chemistry Communications 111 (2020) 107622
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.
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The authors declare that they have no known competing financial
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Supplementary data to this article can be found online at https://
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article including details of synthesis and characterization for all com-
pounds discussed, parameters for kinetic studies, and calculations of
statistical parameters and can be found online.
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