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Elucidating the Key Role of Phosphine

−Sulfonate Ligands in Palladium-Catalyzed
Ethylene Polymerization: Effect of...

Article in ACS Catalysis · August 2016

DOI: 10.1021/acscatal.6b00911

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 Research Article

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Elucidating the Key Role of Phosphine−Sulfonate Ligands in

Palladium-Catalyzed Ethylene Polymerization: Effect of Ligand
Structure on the Molecular Weight and Linearity of Polyethylene
Ryo Nakano,† Lung Wa Chung,‡ Yumiko Watanabe,§ Yoshishige Okuno,§ Yoshikuni Okumura,∥
Shingo Ito,† Keiji Morokuma,*,⊥ and Kyoko Nozaki*,†
†
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku,
Tokyo 113-8656, Japan
‡
Department of Chemistry, South University of Science and Technology of China, Shenzhen 518055, People’s Republic of China
§
Computational Science and Technology Information Center, Showa Denko K.K., 1-1-1 Ohnodai, Midori-ku, Chiba, Chiba 267-0056,
Japan
∥
Institute for Advanced and Core Technology, Showa Denko K.K., 2 Nakanosu, Oita, Oita 870-1809, Japan
⊥
Fukui Institute for Fundamental Chemistry, Kyoto University, 34-4 Takano Nishihiraki-cho, Sakyo, Kyoto 606-8103, Japan
*
S Supporting Information

ABSTRACT: The mechanism of linear polyethylene formation catalyzed by palladium/phosphine−sulfonate and the effect of
the ligand structure on the catalytic performance, such as linearity and molecular weight of the polyethylene, were reinvestigated
theoretically and experimentally. We used dispersion-corrected density functional theory (DFT-D3) to study the entire
mechanism of polyethylene formation from (R2PC6H4SO3)PdMe(2,6-lutidine) (R = Me, t-Bu) and elucidated the key steps that
determine the molecular weight and linearity of the polyethylene. The alkylpalladium ethylene complex is the key intermediate
for both linear propagation and β-hydride elimination from the growing polymer chain. On the basis of the key species, the
effects of substituents on the phosphorus atom (R = t-Bu, i-Pr, Cy, Men, Ph, 2-MeOC6H4, biAr) were further investigated
theoretically to explain the experimental results in a comprehensive manner. Thus, the experimental trend of molecular weights
of polyethylene could be correlated to the ΔΔG⧧ value between (i) the transition state of linear propagation and (ii) the
transition state of the path for ethylene dissociation leading to β-hydride elimination. Moreover, the experimental behavior of the
catalysts under varied ethylene pressure was well explained by our computation on the small set of key species elucidated from
the entire mechanism. In our additional experimental investigations, [o-Ani2PC6H4SO3]PdH[P(t-Bu)3] catalyzed a hydrogen/
deuterium exchange reaction between ethylene and MeOD. The deuterium incorporation from MeOD into the main chain of
polyethylene, therefore, can be explained by the incorporation of deuterated ethylene formed by a small amount of Pd−H
species. These insights into the palladium/phosphine−sulfonate system provide a comprehensive understanding of how the
phosphine−sulfonate ligands function to produce linear polyethylene.
KEYWORDS: phosphine sulfonate, palladium catalysts, ethylene polymerization, linearity, molecular weight,
suppression of β-hydride elimination

1. INTRODUCTION compatibility, especially with polar materials.3 Although early-

Polyolefins such as polyethylene and polypropylene comprise
one of the largest classes of chemicals today.1,2 A longstanding
challenge in polyolefin synthesis is the development of efficient
methods to introduce polar functional groups into the polymer
structure. These polar groups greatly improve material
properties such as adhesion, dye retention, printability, and
transition-metal catalysts used in the industrial production of
polyolefins are heavily deactivated by polar functional groups,
Received: March 30, 2016
Revised: July 5, 2016

© XXXX American Chemical Society 6101 DOI: 10.1021/acscatal.6b00911

ACS Catal. 2016, 6, 6101−6113
ACS Catalysis
recently emerged late-transition-metal complexes have been
revealed to act as catalysts for the copolymerization of polar
monomers directly with ethylene.4,5 Using α-diimine ligated
palladium complexes, coordination−insertion copolymerization
of ethylene with methyl acrylate to produce highly branched
copolymers was first accomplished by Brookhart and co-
workers in 1996.6 In 2002, Drent et al. reported the synthesis of
linear copolymers of ethylene and alkyl acrylates using
palladium/phosphine−sulfonate catalysts.7 Subsequently, the
palladium/phosphine−sulfonate system has been proven to
tolerate a variety of functional groups,8 which successfully
enabled the unique copolymerizations of ethylene with polar
monomers such as acrylates,7,9 acrylic acid,10 acrylonitrile,11
vinyl halides,12 vinyl ethers,13 vinyl acetate,14 and allyl
monomers.15
The differences in the polymer microstructures of poly-
ethylenes prepared by palladium/α-diimine and palladium/
phosphine−sulfonate catalysts are noteworthy (Figure 1).
Figure 1. Differences in polyethylene microstructures obtained by
palladium/α-diimine and palladium/phosphine−sulfonate catalysts.
Palladium/α-diimine catalysts are susceptible to repetitive β-
hydride elimination and reinsertion reactions, commonly
referred to as chain-walking,16 and generally form highly
branched polyolefins. On the other hand, phosphine−sulfonate
ligated palladium complexes produce highly linear polyethylene
in which the linear versus branched ratio in a main chain is
usually more than 1000. In addition to palladium and nickel17
catalysts bearing phosphine−sulfonate ligands, group 10 metal
catalysts that can achieve a comparable level of linear selectivity
are still limited. Nickel/salicylaldiminate18 and SHOP-type
nickel/R2PC6H4O complexes19 with elaborate catalyst tuning
produced highly linear polyethylene. Recently, we also
developed palladium complexes bearing bis(phosphine mon-
oxide) ligands (BPMO)20 or imidazo[1,5-a]quinolin-9-olate-1-
ylidene (IzQO)21 ligands, which produce almost linear
polyethylene with minimum branching.
The unique linear selectivity in polyethylene formation by
the palladium/phosphine−sulfonate system prompted research-
ers to study the reaction mechanism of ethylene polymerization
both experimentally22,23 and theoretically.24,25 From the
experimental side, Jordan and co-workers reported their
attempt to copolymerize 6-chloro-1-hexene with ethylene
using palladium/phosphine−sulfonate catalysts. However, the
microstructure analysis of the obtained polymers suggested the
occurrence of β-chloride elimination from the ω-chloroalkyl-
palladium species, which implied that chain-walking also
proceeded with the palladium/phosphine−sulfonate system.22
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The observation of 1-octene isomerization into internal octenes
by Claverie and co-workers also supported the chain-walking
reactions by palladium/phosphine−sulfonate catalysts.23 From
a theoretical viewpoint, in contrast, Ziegler and co-workers
reported that the β-hydride elimination is slower in comparison
to the polymer-chain growth in the catalyst system.24 In order
to consolidate this discrepancy between the experimental and
computational insights, we previously studied the mechanism of
linear polyethylene formation. 25 On the basis of the
experimental observation of long-alkyl intermediates during
polymerization and the detailed theoretical calculations on the
mechanism of both linear and branched propagation pathways,
we proposed that the chain propagation dominates over β-
hydride elimination in the presence of sufficient ethylene
pressure.
Since our mechanistic studies in 2009, further mechanistic
understanding of the palladium/phosphine−sulfonate system
has been accumulated. The mechanism of cis/trans isomer-
ization, which is the key step prior to the ethylene insertion
reaction, was examined by Jordan and co-workers.26 After the
isolation of cis and trans isomers of alkylpalladium complexes
and kinetic control experiments, they concluded that the
isomerization process does not require neutral ligands such as
pyridine and 2,6-lutidine, as suggested in our previous
computational study. The influence of the fourth monodentate
ligand was scrutinized by Mecking and co-workers.27 Their
study revealed little effect of the fourth ligands on the polymer
microstructure and the ceiling of activity by modification of
such ligands. Moreover, they established an effective access to a
fourth-ligand free active species by in situ activation of the
sodium chloride adduct Na[(R2PC6H4SO3)PdMeCl] with
AgBF4.
The steric effect from the substituents on the phosphorus
atom plays an important role in modulating the molecular
weight of the obtained polyethylene (Figure 2), although the
Figure 2. Substituents on the phosphorus atom effective in increasing
the molecular weight of polyethylene.
exact role of the substituents remains unclear. Systematic
variations of the substituent on the phosphorus atom were
reported by Claverie,28 Jordan,29 Mecking,27c,30 Nozaki,31
Rieger,32 and their co-workers, independently. Generally, the
molecular weight of polyethylene was increased by the steric
protection of the axial orientation of the palladium center. The
highest molecular weight of polyethylene of more than 50000
was accomplished with catalysts bearing Men (menthyl)31a or
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ACS Catalysis
biaryl (2-[2′,6′-(MeO)2C6H3]C6H4) substituents on the
phosphorus atom (Figure 2). This trend has been interpreted
on the basis of the inhibition of the associative chain-transfer
process by the steric protection, which enhances the molecular
weight of polyethylene, in parallel to the aforementioned
palladium/α-diimine complexes in which the blocking of the
axial positions effectively hampers the chain transfer, leading to
the production of polyethylene of high molecular weights
(Scheme 1).33,34 Our previous computational studies,25 which
Scheme 1. Protection of the Axial Orientation of a Palladium
Center Bearing an α-Diimine Ligand, Leading to the
Suppression of Chain Transfer and the Production of High-
Molecular-Weight Polyethylene
focused on highly simplified model complexes bearing Me- or
Ph-substituted phosphine−sulfonate ligands, were unsuccessful
in providing a mechanistic rationale for the steric influence.
Recently, Rezabal and co-workers studied the steric effect of
Me-, Ph-, and ferrocenyl (Fc)-substituted phosphine−sulfonate
ligands.35 They explained the steric effect on the chain length of
polyethylene obtained by probing a pyridine dissociation step
prior to β-hydride elimination.
In addition, deuterium-labeling experiments suggested the
involvement of reversible β-hydride elimination during ethylene
polymerization,36 which was not in accordance with the results
of our previous computation.25 Nozaki and co-workers
observed deuterium incorporation into the main chain of
polyethylene from MeOD as the deuterium source, when
(Cy2PC6H4SO3)PdMe(2,6-lutidine) or [(o-Ani)2PC6H4SO3]-
PdMe(2,6-lutidine) was heated in a mixture of MeOD and
toluene under ethylene pressure (Scheme 2).36 The proposed
Scheme 2. Deuterium Incorporation into the Main Chain of
Polyethylene from MeOD
mechanism for the deuterium incorporation was as follows: the
palladium hydride species formed after β-hydride elimination
from the Pd alkyl species can undergo hydride/deuteride
exchange at the palladium center and return to the polymer-
ization cycle. This proposed mechanism including a reversible
β-hydride elimination reaction during ethylene polymerization
was not compatible with our previous conclusion based on
mechanistic studies claiming that the chain propagation
dominates over β-hydride elimination in the presence of
ethylene pressure.
In the present study, we report a comprehensive mechanistic
rationale for polyethylene formation by the palladium/
phosphine−sulfonate system, which can explain the aforemen-
tioned newly reported observations. In the first part, an in-
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depth computational study on the entire mechanism of
ethylene polymerization using dispersion-corrected density
functional theory (DFT-D3) and a realistic catalyst model
was performed. The study allowed us to determine the key
steps/factors affecting the molecular weight and microstructure
of polyethylene. In the second part, the key steps in the first
part were further examined both experimentally and theoret-
ically with various substituents on the phosphorus atom. The
effect of the substituents was reasonably explained by the
relative energy levels of the key species. In the third part, a new
plausible mechanism of D incorporation into the polyethylene
chain from MeOD was proposed, on the basis of control
experiments and mechanistic considerations.
2. RESULTS AND DISCUSSION
2.1. Entire Free Energy Surface with Improved
Computational Methods and Models. In this computa-
tional study, several points were improved from our previous
computations.25
(1) Instead of the hybrid functional B3LYP, the dispersion-
corrected functional B3LYP-D3 was employed for better
estimation of the coordination energy.37 The solvent effect
(toluene) was also included for all of the species by using the
SMD method.38
(2) Several new transition states and intermediates involved
in the β-hydride elimination step were identified.
(3) In our previous study,25 the palladium/phosphine−sul-
fonate complexes were simplified by replacement of the
substituents on the phosphorus atom by Me groups and 2,6-
lutidine by pyridine, as a model for comprehensive calculation.
In addition to the (Me2PC6H4SO3)Pd(n-propyl)(2,6-lutidine)
complex, we also carried out calculations with a realistic model
of the complex (t-Bu2PC6H4SO3)Pd(n-propyl)(2,6-lutidine).
The results of the theoretical calculation for polyethylene
formation by (R2PC6H4SO3)Pd(n-propyl)(2,6-lutidine) com-
plexes (R = Me, t-Bu) are summarized in Figures 3 and 4,
respectively. In the following discussion, the intermediates are
numbered according to our previous report25 for ease of
comparison. Due to the electronic asymmetry of the
phosphine−sulfonate ligands which consist of a strong donor
motif (phosphine) and a weak donor motif (sulfonate), all the
intermediates and the transition states have a pair of cis and
trans isomers such as 10 and 10′. Substituents on the
phosphorus atom are shown as subscripts such as 10Me and
10t‑Bu, when discrimination is required. The ethylene-
coordinated intermediate 10 was set as the starting complex
according to our previous paper.
Grimme’s dispersion correction (D3) relatively stabilized the
intermediates and transition states bearing neutral ligands, such
as 2,6-lutidine and ethylene (see Scheme S1 and Table S1 in
the Supporting Information for a comparison). On the basis of
Claverie’s experimental observation of high activity for ethylene
homopolymerization,28d t-Bu substituents highly destabilized
resting intermediates 8t‑Bu and 10t‑Bu by a combination of high
steric repulsion and electron-donating ability.
In the following sections, the mechanisms of linear
propagation, β-hydride elimination, and subsequent branch
formation and chain transfer are discussed.
2.1.1. Linear Propagation. Linear polyethylene formation
preferentially proceeds along ethylene-coordinated intermedi-
ate 10, pentacoordinated cis/trans isomerization via TS(10-
10′), and then ethylene insertion via TS(10′-11′) (blue
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Figure 3. Free energy profile of palladium/dimethylphosphine sulfonate catalyst (B3LYP-D3/6-31G*, lanl2dz for palladium) in toluene.
Figure 4. Free energy profile of palladium/di-tert-butylphosphine sulfonate catalyst (B3LYP-D3/6-31G*, lanl2dz for palladium) in toluene.
pathway in Figures 3 and 4), as discussed in our previous
work.25
2.1.2. β-Hydride Elimination. 2.1.2.1. Formation of cis-P−
Pd−H Species 12a′ and 12′. In the dispersion-corrected free
energy surfaces, the most favorable pathway for β-hydride
elimination proceeds along the formation of β-agostic
intermediate 9′ and TS(9′-12a′) (Figures 3 and 4). For this
route, the rates of all the paths for the formation of
intermediate 9′ are much slower than that of the following β-
hydride elimination via TS(9′-12a′).
Three possible types of formation pathways were found for
the formation of intermediate 9′: (1) direct cis/trans
isomerization from β-agostic intermediate 9 to 9′ via TS(9-
9′), (2) the fourth ligand associated cis/trans isomerization via
TS(8-8med)/TS(8med-8′) or TS(10-10′) and subsequent
associative ligand exchange between the β-C−H bond and
ethylene or 2,6-lutidine (via TS(8′-9′) or TS(9′-10′),
respectively), and (3) the fourth ligand associated cis/trans
isomerization, ligand dissociation to three-coordinated inter-
mediate 9NA′ (9′ with no agostic interaction), and following
isomerization to 9′. The contribution of pathway 1 via TS(9-
9′) should be negligible, since it requires much higher
activation energy than pathways 2 and 3 (Figures 3 and 4).
For pathway 2, the key dissociation steps via TS(8′-9′) and
TS(9′-10′) are associative ligand exchange reactions in which
the fourth neutral ligand (2,6-lutidine or ethylene) is replaced
by a β-agostic interaction via five-coordinated transition states.
Therefore, the steric hindrance on the axial orientation of the
palladium center provided by substituents on the phosphorus
atom can retard these processes. The acceleration effect with
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2,6-lutidine is comparable with that of ethylene, considering
that the concentration of ethylene is much higher than that of
2,6-lutidine under sufficient ethylene pressure. The mole
fraction of ethylene in toluene under 3.0 MPa of ethylene
pressure at 90 °C was reported to be 0.20.39 Then, under
typical conditions (0.10 mmol/L of catalyst in toluene and 3.0
MPa of ethylene pressure at 80 °C), the ratio between ethylene
and 2,6-lutidine (=catalyst) in the solvent mixture reaches more
than 2400. When the activity difference between ethylene and
2,6-lutidiene is ignored, the ratio corresponds to ca. 5 kcal/mol
difference. Thus, TS(9′-10′) is the key transition state before β-
hydride elimination under a high ethylene pressure.40
The contribution of pathway 3, which is discussed in this
work for the first time, depends upon the steric pressure from
substituents on the phosphorus atom. With the less hindered
Me-substituted ligand, the relative free energy of intermediate
9NA′Me is higher than that of TS(9′-10′)Me by ca. 2 kcal/mol,
and then the contribution of the type 3 pathway should be
negligible under sufficient ethylene pressure. On the other
hand, with the more sterically demanding t-Bu-substituted
ligand, three-coordinated intermediate 9NA′t‑Bu is more stable
than TS(9′-10′)t‑Bu by ca. 5 kcal/mol, suggesting that this
pathway can contribute even under high pressure of ethylene.
2.1.2.2. Formation of trans-P−Pd−H Species 12a and 12.
Other β-hydride elimination/reinsertion pathways via TS(9-
12a), TS(9a-12), TS(12-13a), and TS(12a-13) were then
discussed for the first time. The difference between 12a and 12
lies in the orientation of the coordinating propylene (see
Figures S28 and S30 in the Supporting Information), and 12a is
more easily accessible. The thermodynamic instability of
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Figure 5. Possible pathways for chain-transfer reaction: (a) R = Me; (b) R = t-Bu.
intermediates 12a and 12 can be attributed to the strong trans
influence from the phosphine donor. The activation barriers of
TS(9-12a) and TS(9a-12) for forming the trans-P−Pd−H
species are higher than that for the main pathway of
polyethylene formation via TS(10′-11′) (shown in blue) by
4−6 kcal/mol due to the thermodynamic instability of the
products and are comparable to that for TS(9′-10′) (which is
the rate-determining step for the formation of the cis-P−Pd−H
species). Therefore, the formation of the trans-P−Pd−H
species should be less plausible, unless under extremely low
concentration of ethylene.
2.1.3. Possible Pathways after β-Hydride Elimination.
2.1.3.1. Linear Propagation, Chain Transfer, and Methyl-
Branch Formation from cis-P−Pd−H Species 12a′ or 12′.
There are three possible pathways from intermediates 12a′ and
12′ (cis-P−Pd−H species), which are formed after β-hydride
elimination from 9′ or 9a′ and in fast equilibrium via TS(12a′-
12′): reinsertion to linear-chain formation (the left side of
Figures 3 and 4), methyl-branch formation (the right side of
Figures 3 and 4), and chain-transfer reactions (Figure 5). When
the three possibilities are compared, the chain-transfer reactions
are more favored than the other two pathways in the cases of
both the Me- and t-Bu-substituted phosphine−sulfonate
ligands. The Me-substituted palladium/phosphine−sulfonate
favors an associative chain transfer via five-coordinated TS(12′-
17′)Me, while the sterically crowded t-Bu-substituted palla-
dium/phosphine−sulfonate favors a dissociative chain transfer
via the three-coordinated intermediate 19′t‑Bu (Figure 5).
Here, the selectivity of linear chain propagation versus
branch formation after β-hydride elimination is discussed. Since
the β-hydride elimination/reinsertion (via TS(9′-12a′)/TS-
(12′-13′)) and propylene rotation (via TS(12a′-12′)) are
relatively fast, the recoordination of ethylene or 2,6-lutidine
toward the β-agostic intermediate 9′ (linear) or 13′ (branched)
determines the selectivity between linear repropagation and
branch formation. In the cases of both Me and t-Bu substituents
on the phosphorus atom, branch formations via TS(13′-14′)
and TS(13′-20′) are slightly lower in energy than the
corresponding linear pathways via TS(9′-10′) and TS(8′-9′).
The relative stabilities of intermediates 9′ and 13′ (13′ is more
stable than 9′ by ca. 3 kcal/mol) agree with this trend. This
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tendency indicates that, once the β-hydride elimination does
take place, there is a better chance of methyl branch formation
if it does not proceed to chain transfer.
2.1.3.2. Linear Propagation and Methyl-Branch Forma-
tion from trans-P−Pd−H Species 12 or 12a. Due to the
thermodynamic inaccessibility of 12 and 12a (trans-P−Pd−H
species), further reactions from those species are less likely to
happen. The possible pathways from 12 and 12a should be
discussed separately, since we could not find the direct
interconversion transition states between intermediates 12
and 12a. When the ethylene is placed coplanar with the
palladium plane, reinsertion of the olefin easily proceeds to re-
form 9 and 9a.
From the more accessible intermediate 12a, further
conversion to methyl branches or chain transfer is less
plausible. The isomerization to branched intermediate 13 via
TS(12a-13) required much greater activation energy in
comparison to the pathway to the linear intermediate 9 via
TS(9-12a) by more than 5 kcal/mol for both of the
substituents on the phosphorus atom. For an associative
chain-transfer reaction, five-coordinated intermediate 18Me was
the intermediate for the transition between 12Me and 17Me
(Figure 5a). On the other hand, with t-Bu substituents, only the
direct transition state TS(12a-17)t‑Bu was found for the
transition between 12t‑Bu and 17t‑Bu (Figure 5a). Given that
the dissociation of each alkene from 18Me requires 1−2 kcal/
mol activation energy, we treated both 18Me and TS(12a-
17)t‑Bu as the barrier for the associative chain-transfer reaction.
While the associative chain-transfer reaction via 18Me seems
feasible with the Me-substituted phosphine−sulfonate ligand
(Figure 5a), the chain-transfer reactions via TS(12a-17)t‑Bu or
via 19 (14-electron intermediate) are highly hindered and
inaccessible with the t-Bu-substituted ligand (Figure 5b).
From the less accessible intermediate 12, on the other hand,
methyl branch formation via TS(12-13a) is faster than the
preceding β-hydride elimination via TS(9a-12), suggesting that
isomerization via 12 cannot be excluded under low pressure of
ethylene.
2.1.4. Consideration I: Linearity of the Polyethylene. In
order to summarize the first part, the key transition states for
linear propagation, β-hydride elimination (BHE), subsequent
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Scheme 3. Selected Key Intermediates and Transition States for Linear Propagation, β-Elimination, Chain-Transfer Reactions,
and Methyl-Branch Formation
methyl-branch formation, and chain-transfer reactions are
shown in Scheme 3. The linear chain of polyethylene is
formed by the linear PE formation cycle involving intermediates
9, 10, 10′, and 11′ (left cycle). Both of the side reactions,
methyl-branch formation and chain-transfer reaction, arise from
the BHE valley involving intermediates 9′, 9a′, 12′, 12a′, 13′,
and 13a′. Due to the electronic asymmetry of the
phosphine−sulfonate ligands, entrance to the BHE valley is
facilitated by a fourth neutral ligand such as ethylene via
TS(10′-9′) or 2,6-lutidine via TS(8′-9′). In the case of a t-Bu
substituent on the phosphorus atom, spontaneous ethylene
dissociation via 9NA′ should be considered for the entry to the
BHE valley as well. After entry into the BHE valley, methyl-
branch formation (right) and chain-transfer reactions (middle)
are feasible pathways. The catalyst goes back to the linear PE
formation cycle after methyl-branch formation (right), and
intermediate 17′ formed after chain-transfer reactions (middle)
can also reinitiate the linear PE formation. In addition to the
pathways from the BHE valley, branch forming via trans-
P−PD−hydride species 12 (upper pathway) cannot be
excluded, especially with the t-Bu substituent on the
phosphorus atom.
Here the linearity of polyethylene prepared by a catalyst is
defined as
linearity = ln(DP of linear chain in polyethylene)
DP of polyethylene
= ln
1(=chain end per chain) + branches per chain
where DP is the degree of polymerization.
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When the branch formation via trans-P−PD−hydride species
12 is negligible, the linearity should reflect the relative rate of
linear propagation via TS(10′-11′) versus frequency of the
entry to the BHE valley, since branch formation and chain-
transfer reactions would be dominant over linear chain
propagation from the BHE valley involving 9′. Therefore, in
the presence of enough ethylene which would diminish the role
of 2,6-lutidine-mediated TS(8′-9′) and ethylene-dissociated
9NA′, the linearity should be in principle proportional to
ΔΔG⧧ between TS(10′-11′) and TS(9′-10′). Under such
conditions, the linearity of polyethylene does not depend on
the ethylene concentration, since both pathways start from the
same intermediate 10′. On the other hand, when the
contribution of the 2,6-lutidine-mediated transition state and
spontaneous ethylene dissociation to enter the BHE valley
becomes significant, the ratios of the methyl-branch formation
and chain-transfer reactions may be affected by the ethylene
pressure.
2.1.5. Consideration II: Molecular Weight of the Poly-
ethylene. The molecular weight of polyethylene is determined
by the frequency of entering the BHE valley and the ratio of the
subsequent olefin reinsertion vs chain transfer. The favorable
mechanism of chain transfer depends on the size of the
substituent on the phosphorus atom, such as Me or t-Bu (vide
infra); some catalysts favor an ethylene-mediated associative
chain transfer via TS(12′-17′), and others favor a dissociative
chain transfer via 19′. If the chain-transfer reactions dominate
over the linear and branch propagation pathways from the BHE
valley, the molecular weight of the obtained polyethylene
without methyl branches is simultaneously determined by the
linearity of the obtained polyethylene in the presence of the
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Table 1. Effect of Substituents on the Phosphorus Atom on Ethylene Polymerization Activity, Molecular Weight, and
Microstructure of Polyethylenea

catalyst conditions result of polymerization

[cat.] ethylene temp activityb methyl branches on methyl branches per
entry R L (mM) (MPa) (°C) (kg mol−1 h−1) Mnc (103) PDIc 1000Cd chain linearitye
1f t-Bu lut 0.10 3.0 80 1860 6.2 4.1 1.0 0.48 5.1
2 t-Bu lut 0.10 1.0 80 663 4.5 6.2 1.2 0.38 4.8

3f i-Pr lut 0.10 3.0 80 641 6.7 2.7 0 0 5.5

4 i-Pr lut 0.10 1.0 80 497 8.4 2.6 0 0 5.7

5f Cy lut 0.10 3.0 80 1150 11 2.4 0 0 6.0

6 Cy lut 0.10 1.0 80 280 12 2.8 0 0 6.1
7g Cy lut 0.10 3.0 80 121 12 2.9 0 0 6.1

8f Men lut 0.10 3.0 80 205 170 1.5 0 0 8.7

9 Men lut 0.10 1.0 80 123 29 3.7 0 0 7.0

10 Ph lut 0.10 3.0 80 533 5.0 2.2 0 0 5.2

11 Ph lut 0.10 1.0 80 167 5.1 2.1 0 0 5.2
12h Ph NaCl 0.046 0.5 80 1820 1.5j 2.2 0.6 0.06 3.9
13 o-Ani lut 0.10 3.0 80 631 14 2.1 0.55 0.53 5.8
14 o-Ani lut 0.10 1.0 80 229 13 2.6 0.83 0.79 5.6
15h o-Ani NaCl 0.039 0.5 80 2750 12j 2.1 3 2.5 4.8

16i biAr py 0.050 2.1 85 1040 230k 3.9 n.r. n.r. (9.0)
17h biAr NaCl 0.034 0.5 80 5330 29j 2.8 0 0 6.9
a
A mixture of catalyst 1 (10 μmol) in toluene (100 mL) was stirred under an ethylene atmosphere (3.0−1.0 MPa) in a 300 mL autoclave for 1.0 h at
80 °C, unless otherwise noted. Abbreviations: Cy, cyclohexyl; Men, (−)-menthyl; o-Ani, 2-MeOC6H4; biAr, 2-[2′,6′-(MeO)2C6H3]C6H4; lut, 2,6-
lutidine; py, pyridine; n.r., not reported. bBased on isolated yields after precipitation with methanol. cMolecular weights determined by size-exclusion
chromatography (SEC) using polystyrene standards and corrected by universal calibration. dThe number of methyl branches determined by
quantitative 13C NMR analyses. eln(DP of linear chain in polyethylene) = ln(MW of polyethylene) − ln(1 + branches per chain) − ln(MW of
ethylene). See also section 2.1 for the definition. Values in parentheses represent that no data for the branch ratio were available. fFrom ref 31. g9.0
equiv of additional lutidine (90 μmol) was added. hFrom ref 27c. iFrom ref 28d. jMolecular weights determined by SEC using polyethylene
standards. kMolecular weights determined by light scattering analysis.

catalysts. On the other hand, catalysts that can form methyl
branches from the BHE valley can form higher molecular
weight polyethylene in comparison to that estimated from their
linearity.
2.2. Effect of Various Substituents on the Phosphorus
Atom on the Key Steps. In order to confirm the theoretical
results obtained in section 2.1, the effects of the substituents
present on the phosphorus atom on the molecular weight and
linearity of the obtained polyethylene were experimentally
examined with varying ethylene pressure. The observed
substituent trend in the experimental study was further studied
theoretically by computing the energetics for the key
intermediates and transition states depicted in Scheme 3.
2.2.1. Experimental Part. The experimental data of ethylene
polymerization with palladium/phosphine−sulfonate catalysts
bearing the alkyl substituents t-Bu, i-Pr, cyclohexyl (Cy), and
menthyl (Men) and aryl substituents Ph, 2-MeOC6H4 (o-Ani),
and 2-[2′,6′-(MeO)2C6H3]C6H4 (biAr) on the phosphorus
atom are summarized in Table 1. The results in entries 1, 3, 5,
7, 8, 12, and 15−17 were taken from the literature (see the
footnotes in Table 1 for the data sources). In addition to the
6107
reported results, we performed the polymerization reaction
under 1.0 MPa of ethylene pressure, in order to probe the
influence of ethylene pressure on the architecture of the
obtained polyethylene.
In Table 1, entries 1 and 2, with t-Bu substituents on the
phosphorus atom, a slight decrease in molecular weight was
observed upon lowering the ethylene pressure. Interestingly, a
slight increase in the branches per chain was observed under a
higher pressure of ethylene (0.48 under 3.0 MPa of ethylene;
0.38 under 1.0 MPa of ethylene). On the other hand, the
catalysts bearing i-Pr (entries 3 and 4) and Cy (entries 5−7)
substituents on the phosphorus atom showed little response to
ethylene pressure, in terms of the molecular weight and
microstructure of polyethylene without methyl branches. It is
noteworthy that the presence of an additional 9 equiv of 2,6-
lutidine which corresponds to a 10 times higher concentration
of 2,6-lutidine did not change the structure of polyethylene
obtained using the palladium catalyst bearing the Cy
substituent on the phosphorus atom (compare entries 5 and
7). Given that the increase of 2,6-lutidine concentration
corresponds to a relative decrease of ethylene concentration,
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the effect of 2,6-lutidine on the microstructure of polyethylene
may be negligible under the experimental conditions in Table 1
(3.0−0.5 MPa of ethylene with 0.10 mM of catalyst). Using
Men substituents on the phosphorus atom (entries 8 and 9),
which can dramatically increase the molecular weight of
polyethylene,31a the molecular weight and linearity of the
obtained polyethylene were decreased by lowering the ethylene
pressure, whereas no detectable methyl branch was formed in
both cases.
In the case of ligands bearing aryl substituents, plentiful
experimental data were provided by many researchers, and even
fourth ligand free conditions were established by Mecking and
co-workers.27b With Ph substituents on the phosphorus atom
(Table 1, entries 10−12), the reported molecular weights and
calculated linearity differed in the studies by different authors,
whereas our experiments (entries 10 and 11) suggest no
dependence on the ethylene pressure. At 5 bar of ethylene
pressure (entry 12), low linearity and formation of a slight
amount of methyl branches were observed by Mecking and co-
workers,27c which suggests the contribution of non-ethylene-
mediated pathways for methyl-branch formation. The intro-
duction of o-Ani substituents on the phosphorus atom (entries
13−15) increased the methyl branches in polyethylene even
under a high pressure of ethylene. The branch-forming nature
was pronounced under lower pressures of ethylene, which led
to the decrease in the linearity of polyethylene but not the
molecular weight. The biAr substituent (entries 16 and 17),
which effectively increases the molecular weight of poly-
ethylene, showed an effect similar to that of the Men
substituent; the molecular weight and linearity of the obtained
polyethylene were decreased by lowering the ethylene pressure.
In a summary of the experimental study in Table 1, the
substituents on the phosphorus atom are classified according to
the linearity and the experimental response to varied ethylene
pressure (Figure 6). The experimental order of linearity was Ph
Figure 6. Classification of the substituents on the phosphorus atom
based on the experimental response to varied ethylene pressure.
≈ t-Bu < o-Ani ≈ i-Pr < Cy < Men < biAr. In terms of the
molecular weight dependence on the ethylene pressure, i-Pr-,
Cy-, Ph-, and o-Ani-substituted catalysts showed no significant
dependence on the ethylene pressure around 1.0−3.0 MPa. On
the other hand, the molecular weights of polyethylene formed
by the catalysts bearing t-Bu, Men, and biAr substituents on the
phosphorus atom were affected by the ethylene pressure even
at 1.0 MPa. For the branch-forming tendency, only o-Ani and t-
Bu substituents can facilitate the formation of an observable
degree of branches even under a high pressure of ethylene,
whereas catalysts bearing i-Pr, Cy, Men, and biAr substituents
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Research Article
on the phosphorus atom did not form methyl-branched
polyethylene even under low ethylene pressure. The Ph-
substituted catalysts exhibited trace branch formation under
low ethylene pressure (0.5 MPa), but the branch number per
chain was as low as 0.06. These experimentally observed
features of each substituent were studied theoretically by
evaluating the energetics of the key species shown in Scheme 3.
2.2.2. Theoretical Part. The results of the computational
study on the key transition states and intermediates listed in
Scheme 3 are summarized in Table 2. In this theoretical study,
the propagating chain end is modeled by n-pentyl instead of n-
propyl for a better estimation of the steric bulkiness from a
wide range of substituents on the phosphorus atom at positions
farther away from the palladium center. For a linear PE
formation cycle, the ethylene insertion reaction via TS(10′-11′)
was the turnover-limiting step with all of the examined
substituents, not the cis/trans isomerization via TS(10−10′).
After entry to the BHE valley, all the substituents examined
seem to favor branch formation or chain transfer in comparison
to linear repropagation, which means that the entry to the BHE
valley should result in the decrease of linearity by methyl-
branch formation or chain termination (compare the rows of
entry to BHE valley, chain transfer, and branch formation in
Table 2). In the following sections, the effect of the substituents
present on the phosphorus atom on the microstructure of
polyethylene classified in Figure 6 is discussed on the basis of
the mechanistic features obtained from Table 2.
2.2.2.1. Substituent Effect on the Linearity. Although the
computational methods employed here do not reach a
quantitative level, the observed experimental linearity of
polyethylene (see the columns of linearity in Table 1)
correlated well with the calculated ΔΔG⧧ values between
TS(10′-11′) and TS(9′-10′) (see the row of linearity in Table
2); the computational trend of linearity is in excellent
agreement with the experimental trend.
experimental: Ph ≈ t ‐Bu < o‐Ani ∼ i‐Pr < Cy
< Men ≈ biAr
computed: Ph < t ‐Bu < o‐Ani < i‐Pr < Cy < Men
< biAr
2.2.2.2. Substituent Effect on the Molecular Weight
Dependence on Ethylene Pressure. The molecular weight
dependence on the ethylene pressure used in the polymer-
ization, which varied with the substituent on the phosphorus
atom (see also Table 1 and Figure 6), could be explained by the
free energy difference between the pathways for the entrance to
the BHE valley, namely ethylene-associated TS(9′-10′) and
spontaneously dissociated 9NA′, and the free energy difference
between the associative and dissociative chain transfers. For the
associative chain transfer, we found not only TS(12′-17′) for
the conversion between 12′ and 17′ but also the pentacoordi-
nated intermediate 18′ structurally similar to TS(12′-17′).
Given that the dissociation of each alkene from 18′ requires 1−
2 kcal/mol activation energy, we treated both TS(12′-17′) and
18′ as the barriers for the associative chain-transfer reaction,
just as we treated 19′ as the barrier for the dissociative chain
transfer. (see also the description about 18Me in section
2.1.3.2).
The catalysts that showed no response to varied ethylene
concentration (R = i-Pr, Cy, Ph, o-Ani) favor the ethylene-
associated TS(9′-10′) for entrance to the BHE valley and 18′
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Table 2. ΔG, ΔG⧧, and ΔΔG⧧ Values of the Key Transition States and Intermediates from the Corresponding 10 (kcal/mol)a
a
B3LYP-D3/6-31G* and lanl2dz for palladium in toluene. The propagating chain end is modeled by n-pentyl with all-anti configuration, instead of
n-propyl for a better estimation of steric bulk at a position farther from the substituents on the phosphorus atom. Abbreviations: E, ethylene; BHE, β-
hydride elimination. Legend: (*) 18′; (**) coordination of ipso carbon was observed.
for chain transfer, rather than dissociative 9NA′ and 19′ (see
the rows of linearity dependence on ethylene pressure,
associative vs dissociative chain transfer in Table 2). Therefore,
all the steps that determine the molecular weight of polymers,
namely chain propagation via TS(10′-11′), the entrance to the
BHE valley via TS(9′-10′), and the chain transfer via 18′,
should show a first-order dependence on ethylene concen-
tration, and thereby the effect of ethylene activity is canceled.
On the other hand, the catalysts that produce lower
molecular weight polyethylene at decreased ethylene pressure
(R = t-Bu, Men, biAr) apparently favor dissociative entry to the
BHE valley via 9NA′ rather than TS(9′-10′) with associated
ethylene (see the row of linearity dependence on ethylene
pressure in Table 2). Therefore, at a lower ethylene pressure
that decelerates the linear propagation cycle, the frequency of
chain transfer can be pronounced.
2.2.2.3. Substituent Effect on Methyl-Branch Formation.
The trend of each catalyst to form methyl branches is discussed
separately on the basis of the classification in Figure 6.
2.2.2.3.1. t-Bu. The catalyst bearing t-Bu substituents on the
phosphorus atom produced slightly branched polyethylene
even under high ethylene pressures (entries 1 and 2 in Table
1). On the basis of the computation in Table 2, the formation
of trans-P−Pd−H species via TS(9a-12) is less likely, since it
required a larger activation energy than the linear propagation
via TS(10′-11′) and the entry to the BHE valley via TS(9′-10′)
or via 9NA′. From the BHE valley, ethylene coordination to
13NA′ to give 14′ proceeds with little activation barrier and is
in competition with associative and dissociative chain transfers.
Therefore, a higher concentration of ethylene may increase the
branches per chain, due to a relative decrease in the rate of
dissociative chain transfer via 19′ and reverse conversion from
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Research Article
14′ to 13NA′. Actually, in the case of the t-Bu substituent, a
slight increase in the methyl branches per chain was
experimentally observed under higher pressures of ethylene.
2.2.2.3.2. i-Pr, Cy, and Ph. The catalysts bearing i-Pr, Cy,
and Ph substituents on the phosphorus atom produced highly
linear polyethylene and showed no response to variations in
ethylene pressure (entries 3−7 and 10−12 in Table 1). On the
basis of the computation in Table 2, the formation of trans-P−
Pd−H species via TS(9a-12) and entry to the BHE valley via
9NA′ are less likely, since those required a larger activation
energy in comparison to the linear propagation via TS(10′-11′)
and entry to the BHE valley via TS(9′-10′). From the BHE
valley, these substituents facilitate both associative chain
transfer via TS(12′-17′) and dissociative path via 19′ over
the branch-forming pathway via TS(13′-14′) and 13NA′.
Hence, little branch formation occurs from the BHE valley.
2.2.2.3.3. o-Ani. The catalyst bearing o-Ani substituents on
the phosphorus atom can produce slightly branched poly-
ethylene even under high ethylene pressure, and the branches
per chain was increased at lower ethylene pressures (entries
13−15 in Table 1). From the computational results in Table 2,
a characteristic of this catalyst is the low-energy TS(9a-12),
comparable to TS(9′-10′), the favored entry to the BHE valley.
Therefore, the branch formation with the catalyst possibly
occurs via the trans-P−Pd−H species 12 (zeroth order to
ethylene pressure) and not via the BHE valley through 9′/9a′
and 12′/12a′. This explanation is consistent with the
experimental observation of increased branches per chain at
lowered ethylene pressure.
2.2.2.3.4. Men and biAr. In the case of Men and biAr
substituents, while the formation of methyl branches was not
experimentally detectable (entries 8, 9, 16, and 17 in Table 1),
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the computational results suggest that methyl-branch formation Scheme 5. Plausible Mechanism of Deuterium Incorporation
after β-hydride elimination is feasible under high pressures of from MeOD into Ethylene42
ethylene. This discrepancy may arise from some overlooked
factors in the small set of calculations, such as conformational
sampling or entropic effects, or uncovered advent effects from
these huge substituents on the phosphorus atom toward chain-
transfer process.
2.2.3. Summary of the Substituent Effect on the
Polyethylene Formation. In section 2.2, the effect of the
substituents present on the phosphorus atom of the palladium/
phosphine−sulfonate catalysts on the mechanism of linear
polyethylene formation was experimentally and theoretically
studied. Experimentally, several polymerization reactions were
carried out under varied ethylene pressures, in order to
investigate the mechanism of linear polyethylene formation.
Theoretically, the key transition states and intermediates in
Scheme 3 were examined with various substituents on the
phosphorus atom. The experimental behaviors of each catalyst,
including linearity, tendency to form methyl branches, and
response to varied ethylene pressure, were qualitatively 23 and the following C−C bond rotation and β-hydride (not
described by the relative free energies of the key species. deuteride) elimination affords 25, having deuterated ethylene.
Therefore, the key species proposed in Scheme 3 are very likely Finally, an ethylene exchange reaction releases the deuterated
to constitute the main catalytic pathways for the linear ethylene and regenerates the starting complex 17′-H.
propagation, β-hydride elimination, chain transfer, and This proposal also leads to an alternative mechanism of
methyl-branch-forming reactions. deuterium incorporation into polyethylene from MeOD, which
2.3. Mechanism of Deuterium Incorporation from is compatible with the mechanism of linear polyethylene
MeOD into Polyethylene: H/D Exchange Reaction of 1- formation detailed in sections 2.1 and 2.2. The palladium−
Alkenes Catalyzed by Palladium Hydride Species. One of hydride species 17′ formed after β-elimination and chain
the questions remaining in our proposed mechanism in Scheme transfer may be able to catalyze deuteration of ethylene as
2 is the mechanism of deuterium incorporation into the main proposed in Scheme 4, before 23 and 24 reinitiate linear
chain of polyethylene from MeOD used as a deuterium source polyethylene formation. Therefore, the deuterium inclusion
(Scheme 2).36 Although reversible β-hydride elimination and into polyethylene from MeOD can be possible via the
H/D exchange reactions during polymerization were proposed formation and incorporation of deuterated ethylene into linear
in the previous paper,36 our computation and experimental polyethylene formation.
observation in sections 2.1 and 2.2 suggest that, once β-hydride When 1-eicosene was used as the substrate for the hydrogen/
elimination occurred, the chain transfer or the branch deuterium exchange reaction, the C1 position of the 1-alkene
formation dominates over the linear propagation. In this part, was slowly but selectively deuterated (Scheme 6). The
we propose an alternative mechanism of deuterium incorpo-
ration, on the basis of the experimental observation of a
Scheme 6. Deuteration of C1 Position of 1-Alkene by a Pd/
hydrogen/deuterium exchange reaction of 1-alkenes catalyzed
Phosphine−Sulfonate Complex
by palladium hydride species.
When a solution of [o-Ani2PC6H4SO3]PdH[P(t-Bu)3]41 (22-
H) in benzene was treated with atmospheric pressure of
ethylene and MeOD, catalytic deuteration of ethylene was
confirmed by quantitative NMR analyses (Scheme 4). On the

Scheme 4. Deuteration of Ethylene by a Palladium/

Phosphine−Sulfonate Complex

selectivity for the C1 position reached ca. 30-fold, which

basis of the partial deuteration of the palladium hydride species
(Scheme 4), as previously observed by Mecking and co-
workers,12b we propose a plausible mechanism for the
deuteration of ethylene (Scheme 5). The starting palladium
hydride complex 22-H undergoes a hydride/deuterium
exchange reaction with MeOD,12b and the phosphine ligand
in 22-D can be replaced by the excess amount of alkenes
present. Once 17′-D was formed, insertion of ethylene to give
6110
could originate from the free energy surface of the BHE valley.
We propose that the insertion of propylene into palladium
hydride species 12a′ or 12′ favors the 2,1-fashion to give 13′,
because 13′ is more stable than 9′ by 2.1 kcal/mol mainly due
to steric effects (Scheme 7). In addition, the 2,1-insertion via
TS(12′-13′) is lower in energy than the 1,2-insertion via
TS(9′-12a′) by 1.0−1.5 kcal/mol for the (R2PC6H4SO3)PdPr
complexes (R = Me, t-Bu) (Figures 3 and 4).
3. CONCLUSION
In this study, we theoretically and experimentally investigated
the mechanism of linear polyethylene formation by palladium/
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ACS Catalysis
Scheme 7. Plausible Explanation for the C1 Selectivity
phosphine−sulfonate catalysts. In the first part, dispersion-
corrected DFT studies on the entire mechanism of poly-
ethylene formation starting from (R2PC6H4SO3)PdMe(2,6-
lutidene) (R = Me, t-Bu) were carried out. Alkylpalladium
ethylene complex 10′ is the key intermediate for both linear
propagation and β-hydride elimination from the growing
polymer chain: ethylene insertion to 10′ for linear propagation
takes place via TS(10′-11′), and β-hydride elimination
proceeds from 9′, which is formed from 10′ either associatively
via five-coordinated TS(9′-10′) or dissociatively via three-
coordinated intermediate 9NA′. Once β-hydride elimination
took place via TS(9′-12a′), associative and dissociative chain-
transfer reactions (via TS(12′-17′) and 19′, respectively)
dominate over the branch formation via TS(13′-14′) and
TS(14′-15′), for both Me- and t-Bu-substituted phosphine−-
sulfonate ligands.
In section 2.2, the effects of various substituents on the
phosphorus atom (R = Me, t-Bu, i-Pr, Cy, Men, Ph, o-Ani,
biAr) were investigated theoretically and experimentally. The
effect of the substituents on the phosphorus atom was classified
by experimentally observed linearity and the response to varied
ethylene pressure. The obtained relative free energies of the key
species proposed in section 2.1 reasonably explained the
experimental behavior of the corresponding catalysts (Figure
6). The linearity of polyethylene was correlated to the relative
activation energy difference between TS(10′-11′) for ethylene
insertion and TS(9′-10′) for ethylene dissociation, both after
cis/trans isomerization. The mechanism of entering the BHE
valley leading to the chain-transfer reaction and branch
formation differed by steric repulsion from substituents on
the phosphorus atom. The catalysts that produce constant
molecular weights of polyethylene under varied ethylene
pressures (i-Pr, Cy, Ph, and o-Ani substituents) were computa-
tionally suggested to favor the ethylene-associated entry to the
BHE valley via TS(10′-11′) and undergo associative chain
transfer. In contrast, the catalysts that showed a dependence on
the ethylene pressures (t-Bu, Men, and biAr substituents)
favored entry into the BHE valley by the spontaneous
dissociation of ethylene via 9NA′. Furthermore, the tendency
of slight methyl-branch formation of t-Bu- and o-Ani-
substituted catalysts was also explained by the energies of a
small set of key transition states.
In section 2.3, we found that [o-Ani2PC6H4SO3]PdH[P(t-
Bu) 3] catalyzed the C-1 selective hydrogen/deuterium
exchange reaction of 1-alkenes using MeOD as the deuterium
source. On the basis of this observation, a new mechanism has
been proposed for the incorporation of deuterium into ethylene
and eventual incorporation of deuterated ethylene, formed by a
small amount of Pd−H species, into the main chain of
polyethylene.
The correspondence of computations and experiments with
various phosphine−sulfonate ligands shows how the unsym-
metric nature of the phosphine−sulfonate ligands affects linear
polyethylene formation with a group 10 metal center (Scheme
8). The combination of a strong and sterically bulky σ donor
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Scheme 8. Role of the Phosphine−Sulfonate Ligand on
Palladium-Catalyzed Linear Polyethylene Formation
and a weak σ donor promotes linear polyethylene formation
after cis/trans isomerization, suppressing (1) the formation of
trans-P−Pd−H species by a strong trans influence from the
phosphine donor (electronic inhibition) and (2) the formation of
cis-P−Pd−H species by retarding the prior ethylene dissocia-
tion (steric inhibition). In the case of the related palladium/α-
diimine catalysts, steric coverage of the axial orientation of the
palladium center was proposed to hinder the associative chain-
transfer process (Scheme 1).33 On the other hand, in the case
of the palladium/phosphine−sulfonate catalysts, steric bulki-
ness provided by substituents on the phosphorus atom can
retard not only the associative chain-transfer process but also
ethylene dissociation via TS(9′-10′) prior to the β-hydride
elimination reaction. The importance of the ethylene
dissociation transition state for linear polyethylene formation
was recently proposed by Jensen in the case of nickel/
salicylaldiminate catalysts.40 Our computation revealed that the
transition states can be controlled by steric inhibition, and the
linearity of polyethylene can be an experimental indicator of the
transition states. The occurrence of the dissociative ethylene
dissociation process via 9NA′, when bulky Men- and biAr-type
substituents are present on the phosphorus atom, represents an
intrinsic limitation of the efforts to block associative ligand
exchange processes but also indicates the possibility of
variability of molecular weights of polyethylene and ethylene/
polar monomer copolymers by tuning reaction conditions.
We believe that the insights obtained here can be the basis
for further in silico modification of the phosphine−sulfonate
ligands and can also help in designing brand-new unsymmetric
ligands for olefin polymerization. Sufficient electronic dis-
symmetry as well as construction of a steric environment
around the strong donor is essential for linear polymerization of
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simple olefins, which is shared in the design of our recent works
on palladium/BPMO20 and palladium/IzQO21 catalysts.
4. COMPUTATIONAL METHODS
All calculations were performed using the Gaussian 09
packages.43 The DFT (B3LYP-D3) methods chosen were
used primarily with 6-31G* basis sets44 for the light atoms and
Lanl2DZ basis sets and effective core potential for palladium.45
All local minima and saddle points were confirmed by their
vibrational frequency calculations (with zero and one imaginary
frequencies, respectively). The saddle points found were
confirmed to be the correct ones by visualizing the vibrational
mode of the imaginary frequency with GaussView. To include
solvation effects (toluene as the solvent), the SMD solvation
model38 was used.
■
ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acscatal.6b00911.
Experimental procedures and full characterization data of
polymers (PDF)
Cartesian coordinates of optimized species and compar-
ison of computational methods (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail for K.M.: morokuma.keiji.3a@kyoto-u.ac.jp.
*E-mail for K.N.: nozaki@chembio.t.u-tokyo.ac.jp.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was partially supported by CREST, JST. The
theoretical calculations were performed using computational
resources provided by the Research Center for Computational
Science, National Institutes of Natural Sciences, Okazaki, Japan.
R.N. is grateful to the Japan Society for the Promotion of
Science (JSPS) for a Research Fellowship for Young Scientists.
■
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DOI: 10.1021/acscatal.6b00911
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ACS Catalysis Research Article

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molecular weights of polyethylene formed by these catalysts are
comparable, the frequency to generate 17′-H should be similar
between these catalysts. Then the degree of deuteration will be
determined by the rate of H/D exchange reaction and the staying
period of 17′-H in the H/D exchange cycle. Because of the similarities
of the alkene exchange TS(25-17′) with TS(12′-17′)/18′ and the

6113 DOI: 10.1021/acscatal.6b00911

ACS Catal. 2016, 6, 6101−6113

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