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Toward the Copolymerization of Propylene with Polar Comonomers

Stephen L. J. Luckham and Kyoko Nozaki*

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CONSPECTUS: Polyolefins are produced in vast amounts and are found in so many consumer products that the two most
commonly produced forms, polyethylene (PE) and polypropylene (PP), fall into the rather sparse category of molecules that are
likely to be known by people worldwide, regardless of their occupation. Although widespread, the further upgrading of their
properties (mechanical, physical, aesthetic, etc.) through the formation of composites with other materials, such as polar polymers,
fibers, or talc, is of huge interest to manufacturers. To improve the affinity of polyolefins toward these materials, the inclusion of
polar functionalities into the polymer chain is essential. The incorporation of a functional group to trigger controlled polymer
degradation is also an emerging area of interest. Currently practiced methods for the incorporation of polar functionalities, such as
post-polymerization functionalization, are limited by the number of compatible polar monomers: for example, grafting maleic
anhydride is currently the sole method for practical functionalization of PP. In contrast, the incorporation of fundamental polar
comonomers into PE and PP chains via coordination insertion polymerization offers good control, making it a highly sought-after
process. Early transition metal catalysts (which are commonly used for the production of PE and PP) display poor tolerance toward
the functional groups within polar comonomers, limiting their use to less-practical derivatives. As late transition metal catalysts are
less-oxophilic and thus more tolerant to polar functionalities, they are ideal candidates for these reactions. This Account focuses on
the copolymerization of propylene with polar comonomers, which remains underdeveloped as compared to the corresponding
reaction using ethylene. We begin with the challenges associated with the regio- and stereoselective insertion of propylene, which is a
particular problem for late transition metal systems because of their propensity to undergo chain walking processes. To overcome
this issue, we have investigated a range of metal/ligand combinations. We first discuss attempts with group 4 and 8 metal catalysts
and their limitations as background, and then focus on the copolymerization of propylene with methyl acrylate (MA) using Pd/
imidazolidine−quinolinolate (IzQO) and Pd/phosphine−sulfonate (PS) precatalysts. Each generated regioregular polymer, but
while the system featuring an IzQO ligand did not display any stereocontrol, that using the chiral PS ligand did. A further difference
was found in the insertion mode of MA: the Pd/IzQO system inserted in a 1,2 fashion, while in the Pd/PS system a 2,1 insertion was
observed. We then move onto recent results from our lab using Pd/PS and Pd/bisphosphine monoxide (BPMO) precatalysts for the
copolymerization of propylene with allyl comonomers. These P-stereogeneic precatalysts generated the highest isotacticity values
reported to date using late transition metal catalysts. This section closes with our work using Earth-abundant nickel catalysts for the
reaction, which would be especially desired for industrial applications: a Ni/phosphine phenolate (PO) precatalyst yielded
regioregular polypropylene with the incorporation of some allyl monomers into the main polymer chain. The installation of a chiral
menthyl substituent on the phosphine allowed for moderate stereoselectivity to be achieved, though the applicable polar monomers
currently remain limited. The Account concludes with a discussion of the factors that affect the insertion mode of propylene and
polar comonomers in copolymerization reactions, beginning with our recent computational study, and finishing with work from
ourselves and others covering both comonomer and precatalyst steric and electronic profiles with reference to the observed
regioselectivity.

■ KEY REFERENCES
• Nakano, R.; Nozaki, K. Copolymerization of Propylene
Received: September 29, 2020

and Polar Monomers Using Pd/IzQO Catalysts. J. Am.

Chem. Soc. 2015, 137, 10934−10937.1 The first report
on the copolymerization of propylene with polar
monomers to give regioregular, atactic copolymers.

© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.accounts.0c00628

A Acc. Chem. Res. XXXX, XXX, XXX−XXX
Accounts of Chemical Research
Figure 1. Selection of fundamental polar monomers that can be used in copolymerization reactions.
Scheme 1. Coordination Insertion Reaction Overview, Highlighting the Benefits Possible with an Optimized System
• Ota, Y.; Ito, S.; Kobayashi, M.; Kitade, S.; Sakata, K.;
Tayano, T.; Nozaki, K. Crystalline Isotactic Polar
Polypropylene from the Palladium-Catalyzed Copoly-
merization of Propylene and Polar Monomers. Angew.
Chem., Int. Ed. 2016, 55, 7505−7509.2 The use of a Pd
complex bearing a chiral phosphine sulfonate ligand
allows for the formation of a highly regioregular,
moderately isotactic copolymer with methyl acrylate.
• Seidel, F. W.; Tomizawa, I.; Nozaki, K. Expedient
Synthetic Identification of a Novel P-Stereogenic Ligand
Motif for the Palladium-Catalyzed Preparation of
Isotactic Polar Polypropylenes. Angew. Chem., Int. Ed.
2020, 10.1002/anie.202009027.3 Our most recent work,
using palladium complexes bearing two different classes
of P-stereogenic ligands. In addition to the formation of
regioregular, isotactic polymers, further computational
experiments allow for a rational explanation as to why
steric bulk is important on the P moiety.
• Konishi, Y.; Tao, W.; Yasuda, H.; Ito, S.; Oishi, Y.;
Ohtaki, H.; Tanna, A.; Tayano, T.; Nozaki, K. Nickel-
Catalyzed Propylene/Polar Monomer Copolymeriza-
tion. ACS Macro Lett. 2018, 7, 213−217.4 A chiral Ni/
phosphine phenolate complex allows for the copoly-
merization of propylene with nonfundamental polar
comonomers to give regioregular, moderately isotactic
polymers.
1. INTRODUCTION
Since its emergence in the early twentieth century, the
development of polymer chemistry has resulted in significant
advances in both science and engineering. This in turn has
directly improved the lifestyles of consumers worldwide, with
applications found in the packaging, automotive, construction,
and medical sectors, among others.5 The two most commonly
used polymers in the world today are polyethylene (PE) and
polypropylene (PP), as has been the case for almost half a
century.6 While PE and PP serve as excellent materials,
industrial and academic groups have long sought to further
improve their properties through the controlled incorporation
of polar functionalities into the otherwise nonpolar polymer
structure. In doing so, the surface properties of the polymer are
enhanced, which makes the synthesis of composites containing
materials such as fibers and talc possible, resulting in improved
and tunable product performance.7 A further advantage that
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has often been overlooked until recently is the improved
prospect of controlled polymer degradation following a
product’s useful lifecycle if the polymer contains polar
functionalities because of the incorporation of heteroatoms.8,9
The most commonly practiced method for the introduction
of polar functionalities into homopolymers (such as PE and
PP) is postpolymerization functionalization.10 While appealing
as no modifications to existing processes to produce
polyolefins are required, the upgrading of alkanes is notoriously
difficult because of their inert C−H bonds. Consequently, side
reactions such as cross-linking and chain-scission are hard to
prevent due to the harsh conditions that these reactions
require.11 This also leads to a lack of control over the final
structure of the functionalized polymer product. A more
elegant solution is the direct copolymerization of the olefin
(for example, ethylene or propylene) with a polar comonomer,
some common examples of which are displayed in Figure 1.
These fundamental polar monomers have a functional group
directly attached to the olefinic double bond and are readily
available as they are already used on a large scale within
industry.12,13 Copolymerization reactions can proceed either
via a radical or a coordination insertion mechanism. The only
systems currently capable of copolymerization reactions using
polar monomers on a commercial scale are radical based.14
However, these processes require elevated temperatures and
pressures (of up to 375 °C and 300 MPa, respectively),
resulting in high costs, in addition to producing highly
branched copolymer products with broad molecular weight
distributions and low crystallinity.10 In contrast, the single site
transition metal catalysts used in coordination insertion
polymerization reactions have the potential to offer a level of
control that makes them highly desirable from an industrial
perspective (Scheme 1), as by limiting branch formation,
highly crystalline polymers can be formed.
As they are well-defined on a molecular level, targeted
catalyst design and subtle alterations therein could potentially
give rise to systems in which polymers are prepared with
desired proportions of comonomer incorporation, at lower
temperatures and pressures than radical polymerizations.
Industrially, the transition metal catalyzed copolymerization
of ethylene with nonpolar monomers is known; however, no
commercial process currently exists for the copolymerization of
olefins with polar monomers,14 due to a series of issues termed
the “polar monomer problem”.15,16 Academically, there have
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Figure 2. Different insertion modes of propylene within a growing polymer chain.
been significant breakthroughs in the copolymerization of
ethylene with fundamental polar comonomers (such as those
displayed in Figure 1) that will not be covered here; readers are
instead directed to recent literature.17,18 This Account will
instead cover the comparatively underdeveloped copolymer-
ization of propylene with polar comonomers. Although this is a
more challenging reaction than the corresponding one with
ethylene, it can elicit polymers with a defined tacticity and
regiochemistry, increasing the number of potential final
applications. A recent review from Marks covers early
transition metal catalyzed systems;19 the focus of this Account
will therefore be on late transition metal catalyzed systems,20
with an emphasis on work from our laboratory.
2. PROPYLENE INSERTION AND SELECTIVITY
To properly frame both the following work and the challenges
that remain in the area, a short overview of aspects regarding
the polymerization of propylene is first presented. As
compared to ethylene, the extra carbon present within
propylene means that insertion into a metal−carbon bond in
either a 1,2 (carbon 1, the terminal carbon, bonds to the metal;
carbon 2, the internal carbon, to the growing polymer chain)
or 2,1 fashion (vice versa) is possible.21 Although 1,2 insertion
is generally favored in both early and late transition metal
systems,22,23 2,1 insertions can occur,24,25 resulting in
variations in the regiochemistry of the resultant polymer
chain (Figure 2).
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Starting from intermediate 1, in which a metal center is π-
coordinated by a molecule of propylene and σ coordinated by
the polymer chain (the last propylene unit of which has
undergone a 1,2 insertion), the insertion of propylene into the
metal−carbon bond in either a 1,2 or a 2,1 mode is possible. In
scenario A, propylene inserts in a 1,2 fashion to give 2, as does
each subsequent unit of propylene, resulting in a head-to-tail
polymer with minimal branching. Following each insertion of
propylene, however, competitive β-hydride elimination and
reinsertion in the opposite manner is possible, for example
from 2 to 4. This leads to the formation of a branch along the
polymer chain in a process known as chain walking, as shown
in scenario B. (Here, a single branched unit is shown due to
space constraints, but it is also possible for the branch to
consist of many units, and for branches to form along
branches.)
Alternatively, a 2,1 insertion of propylene can occur from 1
to give 3, in which the metal is now bonded to a secondary
carbon center. Following the coordination and 1,2 insertion of
propylene, a head to tail defect is found within the chain
(scenario C). Complex 3 is also able to undergo chain walking,
which in this case results in chain straightening after a formal
1,3 insertion (scenario D). While chain walking is possible
after either a 1,2 or 2,1 insertion, it is less likely to take place
following a 1,2 insertion (from complex 2) because of the
kinetic and thermodynamic instability of the tertiary alkene
that is formed as a result of β-H elimination from 2. In
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Figure 3. Common tacticities found within polypropylene chains.

Scheme 2. Copolymerization of Propylene with a Polar Comonomers Using Group 4 Metal Precatalyst33

contrast, following a β-H elimination from the 2,1 insertion
product (complex 3) a primary alkene is formed, which is a
comparatively more favorable process and thus more readily
facilitates chain walking.
Following each insertion of propylene in either a 1,2 or 2,1
mode, a new chiral center is formed in the growing polymer
chain. The stereoregularity of the resulting polymer can be
calculated using quantitative 13C NMR spectroscopy, as the
chemical shift of each methyl carbon in the chain is highly
sensitive to the stereochemistry of its neighboring carbon
atoms (up to 5 monomer units either side of the carbon α to
itself). It is, therefore, possible to quantify the degree of
isotacticity present within the polymer as the probability of
finding consecutive chiral centers with the same (meso, m) or
opposite (racemo, r) absolute configuration. In highly
stereospecific polymers, this can be done to the pentad level
(the chance of finding five consecutive m stereogeneic centers,
mmmm). For less stereoregular polymerizations, the shorter
triad or diad counts (mm and m, respectively) can be used.
This allows for the identification of several different polymer
tacticities, some of which are displayed in Figure 3.
From the above regio- and stereoinsertion modes, there is a
strong industrial preference for high molecular weight
crystalline polymers, meaning that highly active catalysts
capable of giving the isotactic (and less commonly,
syndiotactic) form with minimal branching are sought.26
Early transition metal catalysts (typically d0 metals from
groups 3 and 4) can do this efficiently and have been widely
exploited for the homopolymerization of propylene.27 In
contrast, late transition metal catalysts (typically square planar
d8 nickel or palladium complexes) readily undergo chain
walking and straightening processes unless the reaction
temperature is extremely low (vide infra),28 which have so
far limited their use for the polymerization of propylene.29
and allylamine, masked by aluminum when used in the
presence of excess amount of alkylaluminum reagents.31,32 A
recent example from Marks does not require the use of excess
Lewis acid for the highly isospecific copolymerization of
propylene with an amino olefin bearing a bulky substituent, but
several methylene spacers were required between the amino
and olefin groups, limiting the practicality of the system
(Scheme 2).33
Our laboratory became interested in the use of less oxophilic
metal catalysts to avoid the limitations associated with group 4
metal chemistry as described above. The iron bis(imino)-
pyridine (PDI) complex, 5, in combination with MMAO,
originally reported by Small and Brookhart to give isotactic
polypropylene with excellent tacticity control,22 was used for
the copolymerization of propylene with allyl monomers.
Amorphous polymers with comonomer incorporation of
0.3−2.1% were formed (Scheme 3).34 The polymerization
activity was significantly lowered by the presence of polar
monomers, however, and the applicable polar monomers were
limited to silylated alcohols.
To date, the group 10 metal catalysts reported for propylene
polymerization are inferior to their early transition metal
Scheme 3. Copolymerization of Propylene and Allyl
Monomers Using an Iron(PDI) Complex

3. COPOLYMERIZATION OF PROPYLENE WITH

POLAR COMONOMERS
As early transition metal d0 catalysts (which are highly active in
homopolymerization reactions) possess a low-lying LUMO,30
they are highly oxophilic and, therefore, easily poisoned by
polar functionalities. The comonomers that have been
demonstrated to be compatible with early transition metal
catalysts are protected polar monomers, such as allyl alcohol
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Figure 4. Metal/ligand combinations that have been successfully employed for the copolymerization of propylene with polar comonomers. M =
Pd/Ni; R, R′ = aryl/alkyl/silyl. BArF4 = [B(3,5-(CF3)2C6H3)4]−. Although the Ni/PS example has not been used with propylene, it is worth noting
due to its high activity in copolymerizations with ethylene.35

Table 1. Copolymerization of Propylene with Allyl and Acetate Comonomers Using Either a Pd/IzQO or Pd/PS Precatalyst

entry catalyst (μmol) X (mmol) yield (g) activity (mol/mol h) Mn (×10−3) Mw/Mn incorp. (%) [mm] regiodefects (mol %)
a ,b
1 6 (2) 0.20 808 16 2.2 1.2
2a,c 7 (2) 2.38 235 24 2 0.57 0.9
3b 6 (2) CH2OAc (0.1) 0.08 30.9 3.9 2.2 2.0 1.6
4c 7 (2) CH2OAc (0.46) 0.18 17.8 8.9 2.7 1.7 0.55 1.0
5b,d 6 (10) CO2Me (0.11) 0.04 16.4 3.0 2.2 1.5 - 0.9
6c 7 (10) CO2Me (2.77) 0.20 19.7 4.6 2.2 1.6 0.56 0.9
a
No comonomer added. b0.23 mol of propylene, 20 mL of toluene, 100 °C, 6 h. c0.14 mol of propylene, 10 mL of toluene, 50 °C, 12 h. d3 h.

counterparts regarding tacticity control and activity. They
have, however, shown the requisite tolerance toward polar
functionalities to enable the successful copolymerization of
ethylene with fundamental polar comonomers, to yield polar
functionalized copolymers. Taken together, this suggests that
with the correct catalyst design, the selective copolymerization
of propylene with polar comonomers using late transition
metal catalysts should be possible. The remainder of this
Account covers our efforts toward developing and investigating
these reactions and how the challenges that remain in the area
may be confronted.
The copolymerization of propylene with polar comonomers
using late transition metal catalysts has so far been reported
using the ligand classes displayed in Figure 4.
The first report in the area came from Brookhart, who used
cationic palladium complexes bearing α-diimine ligands to
successfully incorporate either MA or fluorinated octyl acrylate
(FOA) into the resultant polymer.36 The amorphous polymers
formed were highly branched and contained chain straightened
units due to the formal 1,3 insertion of propylene (scenarios B
and D in Figure 2). MA was found to insert in a 2,1 mode and
was mainly located at the branch ends, indicating that its
insertion was followed by chain termination or chain walking.
Neutral α-diimine ligands (which complexed with palladium or
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nickel are known as Brookhart catalysts) have gone on to be
widely exploited across late transition metal catalyzed
polymerizations; however, there are no further reports using
diimine ligands for the copolymerization of propylene. When
taken together with more recent work from Brookhart on the
copolymerization of ethylene with vinylsilanes to give high
molecular weight copolymers with minimal branching,37 this
suggests that the selective insertion of propylene remains
challenging with complexes bearing these ligands because of
their predisposition toward chain walking (β-hydride elimi-
nation followed by reinsertion).28 Indeed, the formation of
highly isotactic polypropylene using a Brookhart catalyst was
shown to be possible by Coates,38 yet required a reaction
temperature of −78 °C, rendering polar commoner incorpo-
ration unfeasible.
In contrast, palladium complexes bearing an asymmetric
anionic bidentate ligand have been shown to effectively
suppress β-hydride elimination from alkylpalladium species.
For example, palladium complexes bearing a phosphine−
sulfonate (PS) ligand (originally reported by Drent in 2002)39
have been used as catalysts to afford highly linear polyethylene
and to copolymerize ethylene with polar comonomers.40
Accordingly, we thought that if by using these palladium
catalysts the insertion mode of propylene could be controlled
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in a 1,2 fashion, it would be possible to obtain regiocontrolled
polypropylene since scenario B in Figure 2 would be avoided.
While examining a variety of unsymmetric bidentate anionic
ligands, we found that palladium complexes bearing an
imidazolium-quinolinolate (IzQO) ligand (complex 6, Table
1) were able to generate regiocontrolled polypropylene, the
first example of a group 10 metal catalyst to do so. By
employing a bulky substituent on the nitrogen atom, a higher
molecular weight polymer with less regio defects was formed,
though the polymer was completely atactic.1 Recently, the use
of a Pd/aIzPy precatalyst was reported by Hong to be active
for the regioselective polymerization of propylene, though no
details regarding stereoselectivity were provided.41
In parallel, we examined the effect of altering the bulky
substituents of the phosphine−sulfonate (PS) ligand in their
corresponding palladium complexes. With the introduction of
two menthyl groups on the phosphorus atom,2 (complex 7,
Table 1), regiocontrolled polypropylene was obtained with a
moderate isotacticity of [mm] = 0.57. The effective protection
of one of the axial sites at the palladium center by the ligand
was suggested to be the reason for the observed regiocontrol,
in addition to the suppression of chain transfer.20 As a
representative example, the number of polymer chains per
catalyst was 10 and the incorporation of polar monomer per
chain was 3.5 units (entry 4, Table 1). With these two classes
of catalysts, the copolymerization of propylene with several
polar monomers, including methyl acrylate (MA), a
fundamental polar monomer, became possible as shown in
Table 1.
As with the homopolymerization, no stereoselectivity was
observed using 6, though 7 was able to produce copolymers
with a value of [mm] of up to 0.56. A 1,2 insertion of both
propylene and allyl acetate was observed using each
precatalyst; however, a different insertion mode of MA was
observed in each case: 1,2 insertion for 6 and 2,1 insertion for
7 (Scheme 4). Notably, the 2,1 MA insertion when 7 was used
results in a head-to-head structure at the junction of propylene
and MA.
Scheme 4. Differing Regioinsertion Modes of MA Using Pd/
IzQO and Pd/PS Precatalysts
This differing regioselectivity is interesting, though it is not
immediately apparent why it is observed. This subject will be
returned to in the final section of this Account along with a
discussion on the factors that dictate which regioinsertion
mode is formed (vide infra).
Very recently, our group has developed two classes of
asymmetric bidentate ligands, each containing a stereogenic
phosphorus atom.3 Using a rapid synthetic protocol, a large
family of Pd/BPMO and Pd/PS catalysts were screened. The
highest isotacticity value among late transition metal catalysts
(disregarding the examples38 which require a very low
temperature, for example, −78 °C) was found using the Pd/
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BPMO system (8, [mm] = up to 0.75), while the Pd/PS
system was also moderately stereoselective (9, [mm] = up to
0.67). Both systems were also able to copolymerize propylene
with allyl comonomers while maintaining their stereoselectivity
(Scheme 5). It should not be overlooked that 8 and 9 are
phosphinite complexes. When an analog of 9 with ArO = 2,6-
Ph2C6H3O is compared with its phosphine counterpart (with
2,6-Ph2C6H3CH2), the tacticity control was about the same
while the phosphine was five times more active than the
phosphinite.3 It is of interest that the copolymerization
reactions using the Pd/BPMO precatalyst 8 in fact displayed
a greater stereoselectivity than the homopolymerized counter-
part. This “comonomer enhanced stereocontrol” was also
noted recently by Marks in Zr-catalyzed copolymerization
reactions,33 and further experiments are ongoing in our
laboratory to establish the rationale behind this surprising
effect.
While good progress has been made in the palladium-
catalyzed copolymerization of olefins with polar monomers,
the corresponding reaction using nickel catalysts is more
attractive because of the cheap and abundant nature of nickel
compared to palladium. Thus, intensive efforts have been
devoted toward this end.42,43 It should be noted, however, that
until 2018 nickel catalysts were hardly applicable to propylene
polymerization due to the low regioselectivity observed. In
2017, Shimizu and co-workers reported a Ni/SHOP type
catalyst for the copolymerization of ethylene and polar
monomers;44 Pan and co-workers have since expanded the
scope of polar comonomers tolerated by the reaction.45
Unfortunately, the SHOP catalysts used in their research,
bearing a triarylphosphine−phenolate ligand, afforded only
short oligomers when propylene was employed instead of
ethylene. We speculated that the low molecular weight
originated from rapid chain-transfer following a 2,1 insertion
of propylene with the Ni/SHOP catalyst. We envisioned that
the bulky alkyl substituent on the P atom within our PS ligand
may be applicable to the SHOP system and could, therefore,
allow for a further improvement regarding the 1,2 regio-control
of propylene insertion. Accordingly, with the well-defined
nickel precatalyst 10, which bears an alkylphosphine-phenolate
(PO) ligand, crystalline copolymers with minimal 1,3 insertion
defects were formed (the less bulky derivative 11 did not
furnish an active system). Comonomer incorporation (up to
1.4%) into the main polypropylene chain was possible, and the
reaction was carried out at a practical temperature of 50 °C
(Table 2).4 A nickel complex bearing a bisphosphine
monoxide (BPMO) ligand in combination with MMAO was
also applicable for the copolymerization of propylene with allyl
acetate, although the copolymerization suffered from poor
activity and low comonomer incorporation.46
Despite affording a highly regioselective system, the
precatalyst 10 was not able to impart any stereoregularity
within the resulting polymer (values of [mm] below 0.20 were
obtained). To improve the stereocontrol of the system, a
precatalyst bearing a ligand with chiral menthyl groups on its
phosphine moiety (12, Table 2) was synthesized. This allowed
for the production of moderately isotactic polymers and
copolymers ([mm] values of up to 0.61 obtained) due to
increased enantiomorphic site control.
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Scheme 5. Homopolymerization of Propylene and the Copolymerization of Propylene with Allyl Monomers Using Pd/PS and
Pd/BPMO Precatalystsa

a
BArF4 = [B(3,5-(CF3)2C6H3)4]−. L = 2,6 lutidine or pyridine.

Table 2. Copolymerization of Propylene and Allyl Monomers Using Nickel/Alkylphosphine−phenolate Complexesa

entry Ni (μmol) R (mmol) activity (mol/mol h) Mn (×10−3) Mw/Mn incorp. (mol %) [mm] regiodefects (mol %)
b,c
1 10 (30) 2614 17 1.8 0.19 0.61
2b 11 (30)
3b 12 197 16 1.8 0.60 7.70
4 10 (20) CH2OH (6.97) 7.12 5.2 1.9 1.4 0.18 0.36
5 10 (10) NHCO2(tBu) (0.76) 11.9 11 1.9 0.39 0.19 0.39
6 10 (20) CH2OAc (1.59) 5.46 7.1 1.3 0.91 0.19 0.80
7 12 (20) CH2OAc (0.81) 42.8 9.1 1.5 0.49 0.61 9.20
a
Conditions: Propylene (237 mmol) toluene (10 mL), 50 °C, reaction time = 12 h. bNo comonomer added, reaction time = 3 h. cThe use of 7
instead of 6 for the homopolymerization of propylene resulted in no polymer product being formed.

4. REGIOINSERTION MODES OF PROPYLENE AND
FUNDAMENTAL POLAR COMONOMERS
The final section of this Account will discuss the factors that
affect the insertion of propylene and polar monomers in
copolymerization reactions between the two. Whether a 1,2 or
2,1 insertion takes place is an important consideration in
copolymerization reactions with propylene (and any other
nonsymmetric alkene) as the insertion mode of the monomer
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can give polymers with different structures and properties. In
the case of propylene 1,2 insertion dominates, but the degree
of regiocontrol depends on the ligand used for the polymer-
ization. Moreover, the choice of ligand can alter the insertion
mode of polar monomers (for example, see the different
insertion modes of MA observed using the Pd/PS and Pd/
IzQO systems displayed in Table 1). Our recent work using P-
stereogenic Pd/BPMO and Pd/PS catalysts (8 and 9, Scheme
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5, and shown again in Figure 5 for clarity) has allowed us to
more clearly define the reasons why, based on their steric
profiles, these ligands are able to deliver stereo- and
regioselective polymers.3
Figure 5. Our recently reported Pd/BPMO and Pd/PS precatalysts,
used as computational models to help understand why they furnish
active systems.
Both classes of catalyst were found to be under
enantiomorphic site control, meaning that the coordination
mode of propylene prior to insertion dictates the resulting
tacticity of the polymer. As the propagating polymer chain
must be trans to the P moiety to be sufficiently activated to
allow for further propagation,47 the coordinated propylene
must be cis to the P atom in the square planar geometry. Thus,
the methyl group of the propylene is sterically repelled by the
bulk of the two R groups on the P center, enforcing a
regioselective 1,2 insertion. It can also be said that these
ligands display a certain electronic preference for 1,2 insertion,
as the use of less bulky derivatives did not result in a large
increase in the proportion of regiodefects (excluding an outlier,
below 5% was recorded in all cases).
The stereoselectivity can be explained through analogy to
group IV metallocene catalysts, which are proposed to enforce
the methyl group on the propylene to align anti with respect to
the growing polymer chain.48,49 Furthermore, these studies
suggest that the relative orientation of the propylene monomer
is less dictated by the steric environment provided by the
ligand itself but rather by the growing polymer chain (whose
orientation is enforced by the sterics of the ligand). We
suggested the same anti orientation to be present in our PS and
BPMO systems, based on the crystal structures of the three
best performing precatalysts (each of which contained a 2,6-
Figure 6. ORTEP structure of Pd/PS precatalyst 9, viewed along two different axes. The purple shading represents the least sterically encumbered
area around the palladium center according to the SamVca 2.1 plot (to be occupied by the growing polymer chain). The green orientation of
propylene is proposed to be more favorable than the red due to less steric pressure from the ligand and growing polymer chain.3
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pubs.acs.org/accounts Article
dimethoxyphenyl group aligned parallel to the Pd square
planar coordination plane; Figure 6) and their corresponding
SamVca 2.1 plots (not shown here). In each case, one face of
the coordination plane is effectively shielded by one of the 2,6-
dimethoxyphenyl groups, rendering it more sterically con-
gested than the other. The growing polymer chain is proposed
to occupy the less sterically congested face (the purple area on
Figure 6), while forcing the methyl group on the propylene to
face the 2,6-dimethoxyphenyl moiety (the green orientation on
Figure 6). Other arrangements of the propylene (as shown by
the red orientations) are less favorable, which we tentatively
suggest to be due to reduced London dispersion interactions.
Together therefore, the steric bulk on the P atom ensures chain
propagation occurs both regio- and stereoselectively.
It has previously been noted for stereoselective acrylate
insertion using Pd/PS complexes that there exists a “window”
within the steric spectrum that allows for regio- and
stereoselectivity to be achieved, and that excessive bulk near
to the Pd center is detrimental.50 This is pertinent in the case
of 8 and 9, where (as shown in Figure 6 and discussed above)
there is a delicate balance between the coordination modes of
propylene within the catalytic pocket. The presence of the
phosphinite oxygen atom in 8 and 9 may allow the ligand to be
positioned so as to provide moderate steric protection close to
the Pd center, while still being able to affect the regio- and
stereoinsertion of propylene.
Regarding the polar comonomers used in these reactions, it
has been demonstrated computationally that for palladium-
alkyl complexes a 2,1 insertion is favored on electronic grounds
when electron-deficient monomers (such as acrylates) are
used, whereas for electron-rich monomers (such as vinyl
ethers) a 1,2 insertion is preferred.51,52 A recent report by
Gordon, Copéret, and co-workers demonstrated that for group
10 metal catalysts the insertion of an olefin into a metal alkyl
bond involves the nucleophilic attack of an occupied
antibonding orbital of π-symmetry of the metal alkyl onto
the π*-orbital of the bound olefin, which eloquently describes
the reason for this differing selectivity.30 In practice, both
insertion modes often take place, and it would be remiss to
apply a one size fits all approach to any system. Stoichiometric
reactions between well-defined complexes and the polar
Acc. Chem. Res. XXXX, XXX, XXX−XXX
Accounts of Chemical Research pubs.acs.org/accounts Article

Figure 7. Different insertion modes of (i) methyl acrylate (MA; Brookhart) and methyl methacrylate (MMA; Sen) into the same cationic
palladium α-diimine complex and (ii) MA into cationic palladium BPMO complexes, with either alkyl or aryl substituents (Nozaki).

monomer function as a useful way of elucidating which is

favored ex situ.
The potentially capricious behavior of polar monomers is
highlighted in Figure 7, where (i) using the same Pd α-diimine
complex, a different insertion mode is observed depending on
whether methyl acrylate (MA) or methyl methacrylate (MMA)
is used36,53 and (ii) altering the ligand shrubbery of Pd
bisphosphine monoxide (BPMO) complexes is shown to give a
different insertion mode of MA.54
While for Figure 7i, it is clear that the bulkier monomer
MMA is prevented from undergoing a 2,1 insertion because of
the methyl substituent, it is less obvious why the differing
regioselectivity is observed in the case of Figure 7ii due to the
similar steric profiles of each ligand. Mecking has more clearly
demonstrated that for palladium complexes bearing diazaphos- Figure 8. Different insertion modes of methyl acrylate (MA) into
pholidine-sulfonate ligands, increasing the bulk of the ligand palladium diazaphospholidine-sulfonate complexes. L = 2,6 lutidine.
leads to an alteration of the regioselectivity of MA insertion
from the preferred 2,1 to a 1,2 mode (Figure 8).55
Although the complexes do not function as active
precatalysts, Figure 8 provides strong evidence that an increase
in the steric bulk of the ligand results in a change in the
regioselectivity of acrylate insertion from 2,1 to 1,2. It is
important to note that either a 1,2 or a 2,1 insertion of polar
monomers can furnish an active catalytic system, as
demonstrated by Brookhart who used palladium and nickel
α-diimine catalysts for the copolymerization of ethylene with
vinylalkoxysilane (Figure 9).37 In each case, active systems
were reported following a predominant 2,1 (nickel) or 1,2
(palladium) insertion of the silane into the metal alkyl bond.
We can now return to the differing regioselectivity observed Figure 9. Work from Brookhart demonstrating a 1,2 or 2,1 insertion
with respect to MA insertion when the precatalysts 6 and 7 are of a vinylsilane into a metal−carbon bond. L = Et2O.
used in copolymerization reactions. As discussed above, the
regioselectivity of MA insertion into palladium-alkyl bonds can fashion. It is tempting to suggest that the difference in
be altered depending on the ligand used, with bulky ligands regioselectivity demonstrated by 6 and 7 is due to an increased
leading to a preferential insertion of polar monomers in a 1,2 steric bulk of the IzQO ligand vis-à-vis the PS. While it is
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Acc. Chem. Res. XXXX, XXX, XXX−XXX
Accounts of Chemical Research
correct that the IzQO ligand present in 6 is indeed bulky, we
have also shown that menthyl-substituted PS ligands, such as
that present in 7, possess significant steric bulk,56 suggesting
that the observed regioselectivity is more nuanced than ligand
steric arguments alone (a 1,2 insertion would otherwise be
expected using 7). It would therefore appear that the electronic
composition of the PS ligand dictates the preferential 2,1
insertion of MA when 7 is used as a precatalyst in the
copolymerization reaction with propylene (Table 1).40 This
highlights the delicate balance that exists between sterics and
electronics when the ligand and monomer within a system are
altered, and serves as a reminder that we do not yet possess
sufficient understanding to confidently predict which regioin-
sertion product will form without a thorough mechanistic
investigation.
5. CONCLUSION AND PERSPECTIVE
As this Account has demonstrated, the copolymerization of
propylene with polar monomers has been accomplished by
palladium and nickel complexes of finely tuned asymmetric
bidentate ligands. Further catalyst development should be
targeted toward improving the activity and tacticity control
offered by these systems, as they remain far behind group 4
metal catalysts in these important areas. Considering its price,
nickel should be the metal of choice for industrial applications,
while further studies on palladium complexes can be used to
further develop our fundamental understanding of these
processes. For industrial applications, the studies on materials
properties (viscosity, rheology, surface, mechanical, etc.) are
also critical.
Although much information was provided by DFT
calculations when we studied the effect of the ligand on the
suppression of β-hydride elimination,45 the design of catalysts
capable of inducing high isotacticity in propylene polymer-
ization is less predictable. There are large number of close
lying, energetically accessible isomeric structures that are
responsible for the observed polymer tacticities. In this regard,
machine learning or a combinatorial approach may better fit
for further catalyst development.
■
AUTHOR INFORMATION
Corresponding Author
Kyoko Nozaki − Department of Chemistry and Biotechnology,
School of Engineering, The University of Tokyo, 113-8656
Tokyo, Japan; orcid.org/0000-0002-0321-5299;
Email: nozaki@chembio.t.u-tokyo.ac.jp
Author
Stephen L. J. Luckham − Department of Chemistry and
Biotechnology, School of Engineering, The University of
Tokyo, 113-8656 Tokyo, Japan; orcid.org/0000-0003-
3732-0668
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.accounts.0c00628
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
J https://dx.doi.org/10.1021/acs.accounts.0c00628
pubs.acs.org/accounts Article
Funding
This work was supported by JST CREST Grant Number
JPMJCR1323, Japan. A part of this work was conducted at the
Research Hub for Advanced Nano Characterization, The
University of Tokyo, supported by MEXT, Japan.
Notes
The authors declare no competing financial interest.
Biographies
Stephen Luckham was born in Manchester, England, in 1991. He
received his M.Chem. degree from the University of Leicester in 2014,
followed by an M.Res. degree (Catalysis) from Cardiff University in
2015. He then moved to the University of Bristol where he undertook
his doctoral studies under the guidance of Prof. Robin Bedford,
followed by a postdoctoral position in collaboration with Victrex plc.
In 2019, he joined the group of Prof. Kyoko Nozaki at the University
of Tokyo as a postdoctoral fellow.
Kyoko Nozaki was born in Osaka, Japan, and graduated from Kyoto
University with a B.Sc. degree in 1986. She received her Ph.D. in 1991
from the same university under the guidance of Prof. Kiitiro Utimoto.
During her Ph.D. studies, she joined Prof. Clayton H. Heathcock’s
group at the University of California, Berkeley, as an exchange student
for 1 year in 1988. Since 1991, she has been a faculty member at
Kyoto University, moved to the University of Tokyo in 2002, and has
been a Professor at the University of Tokyo since 2003. Her research
interests are focused on the development of homogeneous catalysts
for polymer synthesis and organic synthesis.
■
ACKNOWLEDGMENTS
The authors are grateful to Prof. Shingo Ito (Nanyang
Technological University, Singapore), Dr. Yusuke Ota (ETH,
Zürich), and Mr. Falk W. Seidel (The University of Tokyo) for
careful proof reading and valuable suggestions.
■ REFERENCES
(1) Nakano, R.; Nozaki, K. Copolymerization of Propylene and
Polar Monomers Using Pd/IzQO Catalysts. J. Am. Chem. Soc. 2015,
137, 10934−10937.
(2) Ota, Y.; Ito, S.; Kobayashi, M.; Kitade, S.; Sakata, K.; Tayano, T.;
Nozaki, K. Crystalline Isotactic Polar Polypropylene from the
Palladium-Catalyzed Copolymerization of Propylene and Polar
Monomers. Angew. Chem., Int. Ed. 2016, 55, 7505−7509.
(3) Seidel, F. W.; Tomizawa, I.; Nozaki, K. Expedient Synthetic
Identification of a Novel P-Stereogenic Ligand Motif for the
Palladium-Catalyzed Preparation of Isotactic Polar Polypropylenes.
Angew. Chem., Int. Ed. 2020, DOI: 10.1002/anie.202009027.
(4) Konishi, Y.; Tao, W.; Yasuda, H.; Ito, S.; Oishi, Y.; Ohtaki, H.;
Tanna, A.; Tayano, T.; Nozaki, K. Nickel-Catalyzed Propylene/Polar
Monomer Copolymerization. ACS Macro Lett. 2018, 7, 213−217.
(5) Millet, H.; Vangheluwe, P.; Block, C.; Sevenster, A.; Garcia, L.;
Antonopoulos, R. The Nature of Plastics and Their Societal Usage. In
Plastics and the Environment; The Royal Society of Chemistry, 2019;
pp 1−20.
(6) Stürzel, M.; Mihan, S.; Mülhaupt, R. From Multisite Polymer-
ization Catalysis to Sustainable Materials and All-Polyolefin
Composites. Chem. Rev. 2016, 116, 1398−1433.
(7) Goodall, B. L. Late Transition Metal Catalysts for the
Copolymerization of Olefins and Polar Monomers. In Metal Catalysts
in Olefin Polymerization; Guan, Z., Ed.; Springer: Berlin, 2009; pp
159−178.
(8) Wang, X.; Seidel, F. W.; Nozaki, K. Synthesis of Polyethylene
with In-Chain α,β-Unsaturated Ketone and Isolated Ketone Units:
Pd-Catalyzed Ring-Opening Copolymerization of Cyclopropenone
with Ethylene. Angew. Chem., Int. Ed. 2019, 58, 12955−12959.
Acc. Chem. Res. XXXX, XXX, XXX−XXX
Accounts of Chemical Research
(9) Morgen, T. O.; Baur, M.; Göttker-Schnetmann, I.; Mecking, S.
Photodegradable Branched Polyethylenes from Carbon Monoxide
Copolymerization under Benign Conditions. Nat. Commun. 2020, 11,
3693.
(10) Franssen, N. M. G.; Reek, J. N. H.; de Bruin, B. Synthesis of
Functional ‘Polyolefins’: State of the Art and Remaining Challenges.
Chem. Soc. Rev. 2013, 42, 5809−5832.
(11) Boaen, N. K.; Hillmyer, M. A. Post-Polymerization Function-
alization of Polyolefins. Chem. Soc. Rev. 2005, 34, 267−275.
(12) Nakamura, A.; Ito, S.; Nozaki, K. Coordination−Insertion
Copolymerization of Fundamental Polar Monomers. Chem. Rev.
2009, 109, 5215−5244.
(13) Monomers in which there are one or more methylene spacer
groups between the olefin and the functional group are also used in
copolymerization reactions and can possess useful material properties
in the polymer product but are less industrially relevant.
(14) Jeremic, D. Polyethylene. In Ullmann’s Encyclopedia of Industrial
Chemistry; American Cancer Society, 2014; pp 1−42.
(15) Jordan, R. F. Progress on the Polar Monomer Problem. Polym.
Prepr. 2007, 48, 196−197.
(16) Keyes, A.; Basbug Alhan, H. E.; Ordonez, E.; Ha, U.; Beezer, D.
B.; Dau, H.; Liu, Y.-S.; Tsogtgerel, E.; Jones, G. R.; Harth, E. Olefins
and Vinyl Polar Monomers: Bridging the Gap for Next Generation
Materials. Angew. Chem., Int. Ed. 2019, 58, 12370−12391.
(17) Dall’Anese, A.; Rosar, V.; Cusin, L.; Montini, T.; Balducci, G.;
D’Auria, I.; Pellecchia, C.; Fornasiero, P.; Felluga, F.; Milani, B.
Palladium-Catalyzed Ethylene/Methyl Acrylate Copolymerization:
Moving from the Acenaphthene to the Phenanthrene Skeleton of α-
Diimine Ligands. Organometallics 2019, 38, 3498−3511.
(18) Tan, C.; Chen, C. Emerging Palladium and Nickel Catalysts for
Copolymerization of Olefins with Polar Monomers. Angew. Chem., Int.
Ed. 2019, 58, 7192−7200.
(19) Marks, T. J.; Chen, J.; Gao, Y. Early Transition Metal Catalysis
for Olefin-Polar Monomer Copolymerization. Angew. Chem., Int. Ed.
2020, 59, 14726−14735.
(20) Ito, S. Palladium-Catalyzed Homo- and Copolymerization of
Polar Monomers: Synthesis of Aliphatic and Aromatic Polymers. Bull.
Chem. Soc. Jpn. 2018, 91, 251−261.
(21) The inductive effect of the methyl group as compared to a
hydrogen atom also alters the energies of the HOMO and LUMO
orbitals.
(22) Kawamura-Kuribayashi, H.; Koga, N.; Morokuma, K. An Ab
Initio MO Study on Ethylene and Propylene Insertion into the
Titanium-Methyl Bond in CH3TiCl2+ as a Model of Homogeneous
Olefin Polymerization. J. Am. Chem. Soc. 1992, 114, 2359−2366.
(23) Michalak, A.; Ziegler, T. Stochastic Simulations of Polymer
Growth and Isomerization in the Polymerization of Propylene
Catalyzed by Pd-Based Diimine Catalysts. J. Am. Chem. Soc. 2002,
124, 7519−7528.
(24) Small, B. L.; Brookhart, M. Polymerization of Propylene by a
New Generation of Iron Catalysts: Mechanisms of Chain Initiation,
Propagation, and Termination. Macromolecules 1999, 32, 2120−2130.
(25) Hustad, P. D.; Tian, J.; Coates, G. W. Mechanism of Propylene
Insertion Using Bis(Phenoxyimine)-Based Titanium Catalysts: An
Unusual Secondary Insertion of Propylene in a Group IV Catalyst
System. J. Am. Chem. Soc. 2002, 124, 3614−3621.
(26) Because of their faster rates of crystallization during injection
molding, the isotactic form is preferred in industry.
(27) Resconi, L.; Cavallo, L.; Fait, A.; Piemontesi, F. Selectivity in
Propene Polymerization with Metallocene Catalysts. Chem. Rev. 2000,
100, 1253−1346.
(28) Guo, L.; Dai, S.; Sui, X.; Chen, C. Palladium and Nickel
Catalyzed Chain Walking Olefin Polymerization and Copolymeriza-
tion. ACS Catal. 2016, 6, 428−441.
(29) It has recently been demonstrated that the insertion of an
alkene into a metal carbon bond, as takes place during chain
propagation within polymerization reactions, must be considered to
occur via fundamentally different mechanisms for d0 and d8 systems.
(see ref 30).
K https://dx.doi.org/10.1021/acs.accounts.0c00628
pubs.acs.org/accounts Article
(30) Bumberger, A. E.; Gordon, C. P.; Trummer, D.; Copéret, C.
C−H Activation and Olefin Insertion in D8 and D0 Complexes: Same
Elementary Steps, Different Electronics. Helv. Chim. Acta 2020, 103,
e1900278.
(31) Imuta, J.; Kashiwa, N.; Toda, Y. Catalytic Regioselective
Introduction of Allyl Alcohol into the Nonpolar Polyolefins:
Development of One-Pot Synthesis of Hydroxyl-Capped Polyolefins
Mediated by a New Metallocene IF Catalyst. J. Am. Chem. Soc. 2002,
124, 1176−1177.
(32) Hagihara, H.; Tsuchihara, K.; Sugiyama, J.; Takeuchi, K.;
Shiono, T. Copolymerization of Propylene and Polar Allyl Monomer
with Zirconocene/Methylaluminoxane Catalyst: Catalytic Synthesis of
Amino-Terminated Isotactic Polypropylene. Macromolecules 2004, 37,
5145−5148.
(33) Huang, M.; Chen, J.; Wang, B.; Huang, W.; Chen, H.; Gao, Y.;
Marks, T. J. Polar Isotactic and Syndiotactic Polypropylenes by
Organozirconium-Catalyzed Masking-Reagent-Free Propylene and
Amino−Olefin Copolymerization. Angew. Chemie Int. Ed. 2020, 59
(46), 20522−20528.
(34) Kawakami, T.; Ito, S.; Nozaki, K. Iron-Catalysed Homo- and
Copolymerisation of Propylene: Steric Influence of Bis(Imino)-
Pyridine Ligands. Dalt. Trans. 2015, 44, 20745−20752.
(35) Chen, M.; Chen, C. Rational Design of High-Performance
Phosphine Sulfonate Nickel Catalysts for Ethylene Polymerization
and Copolymerization with Polar Monomers. ACS Catal. 2017, 7,
1308−1312.
(36) Johnson, L. K.; Mecking, S.; Brookhart, M. Copolymerization
of Ethylene and Propylene with Functionalized Vinyl Monomers by
Palladium(II) Catalysts. J. Am. Chem. Soc. 1996, 118, 267−268.
(37) Chen, Z.; Brookhart, M. Exploring Ethylene/Polar Vinyl
Monomer Copolymerizations Using Ni and Pd α-Diimine Catalysts.
Acc. Chem. Res. 2018, 51, 1831−1839.
(38) Cherian, A. E.; Rose, J. M.; Lobkovsky, E. B.; Coates, G. W. A
C2-Symmetric, Living α-Diimine Ni(II) Catalyst: Regioblock
Copolymers from Propylene. J. Am. Chem. Soc. 2005, 127, 13770−
13771.
(39) Drent, E.; van Dijk, R.; van Ginkel, R.; van Oort, B.; Pugh, R. I.
Palladium Catalysed Copolymerisation of Ethene with Alkylacrylates:
Polar Comonomer Built into the Linear Polymer Chain. Chem.
Commun. 2002, 744−745.
(40) Nakamura, A.; Anselment, T. M. J.; Claverie, J.; Goodall, B.;
Jordan, R. F.; Mecking, S.; Rieger, B.; Sen, A.; van Leeuwen, P. W. N.
M.; Nozaki, K. Ortho-Phosphinobenzenesulfonate: A Superb Ligand
for Palladium-Catalyzed Coordination−Insertion Copolymerization
of Polar Vinyl Monomers. Acc. Chem. Res. 2013, 46, 1438−1449.
(41) Park, D.-A.; Byun, S.; Ryu, J. Y.; Lee, J.; Lee, J.; Hong, S.
Abnormal N-Heterocyclic Carbene−Palladium Complexes for the
Copolymerization of Ethylene and Polar Monomers. ACS Catal.
2020, 10, 5443−5453.
(42) Mu, H.; Pan, L.; Song, D.; Li, Y. Neutral Nickel Catalysts for
Olefin Homo- and Copolymerization: Relationships between Catalyst
Structures and Catalytic Properties. Chem. Rev. 2015, 115, 12091−
12137.
(43) Mecking, S.; Schnitte, M. Neutral Nickel(II) Catalysts: From
Hyperbranched Oligomers to Nanocrystal-Based Materials. Acc.
Chem. Res. 2020, 53, 2738.
(44) Xin, B. S.; Sato, N.; Tanna, A.; Oishi, Y.; Konishi, Y.; Shimizu,
F. Nickel Catalyzed Copolymerization of Ethylene and Alkyl
Acrylates. J. Am. Chem. Soc. 2017, 139, 3611−3614.
(45) Zhang, Y.; Mu, H.; Pan, L.; Wang, X.; Li, Y. Robust Bulky
[P,O] Neutral Nickel Catalysts for Copolymerization of Ethylene with
Polar Vinyl Monomers. ACS Catal. 2018, 8, 5963−5976.
(46) Jung, J.; Yasuda, H.; Nozaki, K. Copolymerization of Nonpolar
Olefins and Allyl Acetate Using Nickel Catalysts Bearing a Methylene-
Bridged Bisphosphine Monoxide Ligand. Macromolecules 2020, 53,
2547−2556.
(47) Nakano, R.; Chung, L. W.; Watanabe, Y.; Okuno, Y.; Okumura,
Y.; Ito, S.; Morokuma, K.; Nozaki, K. Elucidating the Key Role of
Phosphine−Sulfonate Ligands in Palladium-Catalyzed Ethylene
Acc. Chem. Res. XXXX, XXX, XXX−XXX
Accounts of Chemical Research pubs.acs.org/accounts Article

Polymerization: Effect of Ligand Structure on the Molecular Weight

and Linearity of Polyethylene. ACS Catal. 2016, 6, 6101−6113.
(48) Cavallo, L.; Guerra, G.; Vacatello, M.; Corradini, P. A Possible
Model for the Stereospecificity in the Syndiospecific Polymerization
of Propene with Group 4a Metallocenes. Macromolecules 1991, 24,
1784−1790.
(49) Dahlmann, M.; Erker, G.; Nissinen, M.; Fröhlich, R. Direct
Experimental Observation of the Stereochemistry of the First Propene
Insertion Step at an Active Homogeneous Single-Component
Metallocene Ziegler Catalyst. J. Am. Chem. Soc. 1999, 121, 2820−
2828.
(50) Neuwald, B.; Caporaso, L.; Cavallo, L.; Mecking, S. Concepts
for Stereoselective Acrylate Insertion. J. Am. Chem. Soc. 2013, 135,
1026−1036.
(51) Szabo, M. J.; Jordan, R. F.; Michalak, A.; Piers, W. E.; Weiss, T.;
Yang, S.-Y.; Ziegler, T. Polar Copolymerization by a Palladium−
Diimine-Based Catalyst. Influence of the Catalyst Charge and Polar
Substituent on Catalyst Poisoning and Polymerization Activity. A
Density Functional Theory Study. Organometallics 2004, 23, 5565−
5572.
(52) von Schenck, H.; Strömberg, S.; Zetterberg, K.; Ludwig, M.;
Åkermark, B.; Svensson, M. Insertion Aptitudes and Insertion
Regiochemistry of Various Alkenes Coordinated to Cationic (σ-
R)(Diimine)Palladium(II) (R = − CH3, − C6H5). A Theoretical
Study. Organometallics 2001, 20, 2813−2819.
(53) Borkar, S.; Yennawar, H.; Sen, A. Methacrylate Insertion into
Cationic Diimine Palladium(II)−Alkyl Complexes and the Synthesis
of Poly(Alkene-Block-Alkene/Carbon Monoxide) Copolymers. Orga-
nometallics 2007, 26, 4711−4714.
(54) Mitsushige, Y.; Carrow, B. P.; Ito, S.; Nozaki, K. Ligand-
Controlled Insertion Regioselectivity Accelerates Copolymerisation of
Ethylene with Methyl Acrylate by Cationic Bisphosphine Monoxide−
Palladium Catalysts. Chem. Sci. 2016, 7, 737−744.
(55) Wucher, P.; Roesle, P.; Falivene, L.; Cavallo, L.; Caporaso, L.;
Göttker-Schnetmann, I.; Mecking, S. Controlled Acrylate Insertion
Regioselectivity in Diazaphospholidine-Sulfonato Palladium(II) Com-
plexes. Organometallics 2012, 31, 8505−8515.
(56) Ota, Y.; Ito, S.; Kuroda, J.; Okumura, Y.; Nozaki, K.
Quantification of the Steric Influence of Alkylphosphine−Sulfonate
Ligands on Polymerization, Leading to High-Molecular-Weight
Copolymers of Ethylene and Polar Monomers. J. Am. Chem. Soc.
2014, 136, 11898−11901.

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