molecules

Article
Highly Linear Polyethylenes Achieved Using
Thermo-Stable and Efficient Cobalt Precatalysts
Bearing Carbocyclic-Fused NNN-Pincer Ligand
Jingjing Guo 1,2 , Zheng Wang 2 , Wenjuan Zhang 1, *, Ivan I. Oleynik 3, * ,
Arumugam Vignesh 2 , Irina V. Oleynik 3 , Xinquan Hu 4, *, Yang Sun 2 and Wen-Hua Sun 2, *
1 Beijing Key Laboratory of Clothing Materials R&D and Assessment, Beijing Engineering Research Center of
Textile Nanofiber, School of Materials Science and Engineering, Beijing institute of Fashion Technology,
Beijing 100029, China; [email protected]
2 Key Laboratory of Engineering Plastics and Beijing National Laboratory for Molecular Science, Institute of
Chemistry, Chinese Academy of Sciences, Beijing 100190, China; [email protected] (Z.W.);
[email protected] (A.V.); [email protected] (Y.S.)
3 N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Pr. Lavrentjeva 9, Novosibirsk 630090, Russia;
[email protected]
4 College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China
* Correspondence: [email protected] (W.Z.); [email protected] (I.I.O.); [email protected] (X.H.);
[email protected] (W.-H.S.); Tel.: +86-10-62659707 (W.Z.); +7-383-330-9524 (I.I.O.); +86-571-88320103 (X.H.);
+86-10-6255-7955 (W.-H.S.)

Academic Editor: Giovanni Ricci




Received: 13 March 2019; Accepted: 21 March 2019; Published: 25 March 2019

Abstract: Six examples of 2-(1-arylimino)ethyl-9-arylimino-5,6,7,8-tetrahydrocycloheptapyridine-

cobalt(II) chloride complexes, [2-(1-ArN)C2 H3 -9-ArN-5,6,7,8-C5 H8 C5 H3 N]CoCl2 ,
(Ar = 2-(C5 H9 )-6-MeC6 H3 Co1, 2-(C6 H11 )-6-MeC6 H3 Co2, 2-(C8 H15 )-6-MeC6 H3 Co3,
2-(C5 H9 )-4,6-Me2 C6 H2 Co4, 2-(C6 H11 )-4,6-Me2 C6 H2 Co5, and 2-(C8 H15 )-4,6-Me2 C6 H2 Co6),
were synthesized by the direct reaction of the corresponding ortho-cycloalkyl substituted
carbocyclic-fused bis(arylimino)pyridines (L1–L6) and cobalt(II) chloride in ethanol with good
yields. All the synthesized ligands (L1–L6) and their corresponding cobalt complexes (Co1–Co6)
were fully characterized by FT-IR, 1 H/13 C-NMR spectroscopy and elemental analysis. The crystal
structure of Co2 and Co3 revealed that the ring puckering of both the ortho-cyclohexyl/cyclooctyl
substituents and the one pyridine-fused seven-membered ring; a square-based pyramidal geometry is
conferred around the metal center. On treatment with either methylaluminoxane (MAO) or modified
methylaluminoxane (MMAO), all the six complexes showed high activities (up to 4.09 × 106 g of PE
mol−1 (Co) h−1 ) toward ethylene polymerization at temperatures between 20 ◦ C and 70 ◦ C with the
catalytic activities correlating with the type of ortho-cycloalkyl substituent: Cyclopentyl (Co1 and
Co4) > cyclohexyl (Co2 and Co5) > cyclooctyl (Co3 and Co6) for either R = H or Me and afforded
strictly linear polyethylene (Tm > 130 ◦ C). The narrow unimodal distributions of the resulting
polymers are consistent with single-site active species for the precatalyst. Furthermore, compared
to the previously reported cobalt analogues, the titled precatalysts exhibited good thermo-stability
(up to 70 ◦ C) and possessed longer lifetime along with a higher molecular weight of PE (Mw :
9.2~25.3 kg mol−1 ).

Keywords: highly linear polyethylene; vinyl-end polyethylene; cobalt precatalyst; thermo-stable and
efficient catalysis; correlation between structure and activity

Molecules 2019, 24, 1176; doi:10.3390/molecules24061176 www.mdpi.com/journal/molecules

Molecules
Molecules 2019,
2019, 24,
24, x
1176 22of
of 20
20

Over the past two decades ago, Brookhart [1,2] and Gibson [3–5] independently discovered the
1. Introduction
well‐defined bis(imino)pyridine‐cobalt and ‐iron complexes (A) as highly active precatalysts for
ethylene
Over oligo‐/polymerization.
the past two decades ago, In Brookhart
the intervening[1,2] andyears,
Gibson large
[3–5]numbers of different
independently skeletal
discovered the
modifications, such as changes to the N‐aryl groups and the backbone of pyridine,
well-defined bis(imino)pyridine-cobalt and -iron complexes (A) as highly active precatalysts for ethylene have been made
to the bis(imino)pyridine
oligo-/polymerization. In thescaffolds
intervening (A,years,
Chart 1) numbers
large [6–15], culminating in improvements
of different skeletal modifications,to both
such as
catalytic activity and thermal stability [6,16–33]. The related progress
changes to the N-aryl groups and the backbone of pyridine, have been made to the bis(imino)pyridine was collected in several
reviews
scaffolds[6,9–11,14,15].
(A, Chart 1) [6–15], culminating in improvements to both catalytic activity and thermal
stability [6,16–33].the
To enhance Thethermal
related stability,
progress was one collected
efficient inmethod
severalwas introduced
reviews to the bulky substituent
[6,9–11,14,15].
on theTo enhance the thermal stability, one efficient method was introduced to thehave
ortho‐position of N‐aryl group [6–15] (Chart 1). Wu’s group bulky reported
substituentthat on
bis(imino)pyridine iron complexes (A1) bearing a bulky 2‐methyl‐6‐sec‐phenethyl
the ortho-position of N-aryl group [6–15] (Chart 1). Wu’s group have reported that bis(imino)pyridine group, can
produce linear high
iron complexes (A1)molecular
bearing aweight bulky polyethylene with higher group,
2-methyl-6-sec-phenethyl activitycanat elevated
producetemperature
linear high
[31]. In the recent five years or so, our
molecular weight polyethylene with higher activity at elevated temperature [31]. In thesubstituted
group have developed series of dibenzhydryl recent five
bis(imino)pyridyl iron and cobalt complexes (A2) that displayed
years or so, our group have developed series of dibenzhydryl substituted bis(imino)pyridyl iron good catalytic activity at high
and
temperature
cobalt complexes (A2) that displayed good catalytic activity at high temperature and explored aabout
and explored a very good thermal stability [34]. There were also reports very
incorporating the cycloalkyl
good thermal stability [34]. There substituents
were also reportsin theabout 2,6‐positions
incorporating of the
the cycloalkyl
N‐aryl groups of the
substituents in
bis(imino)pyridine (A3) and it has been found to efficiently increase the temperature
the 2,6-positions of the N-aryl groups of the bis(imino)pyridine (A3) and it has been found to efficiently stability of the
iron
increasecatalysts over their
the temperature alkyl
stability of theanalogues [35]. over
iron catalysts Later
theirRussia’s group [35].
alkyl analogues documented
Later Russia’s the
2,6‐bis(arylimino)pyridy liron(II) chloride complexes by the
group documented the 2,6-bis(arylimino)pyridy liron(II) chloride complexes by the introduction introduction of cycloaliphatic
substituents
of cycloaliphaticinto the ortho position
substituents into of thetheortho
aryl position
groups substantially enlarges
of the aryl groups the temperature
substantially interval
enlarges the
of
temperature interval of efficient use of the related catalysts for ethylene polymerization reactionsthey
efficient use of the related catalysts for ethylene polymerization reactions [36]. Consequently, [36].
have prepared they
Consequently, the multifunctional
have prepared the bis(imino)pyridine iron chloride complexes
multifunctional bis(imino)pyridine incorporating
iron chloride complexes the
cycloalkyl substituent that could display more efficient ethylene polymerization
incorporating the cycloalkyl substituent that could display more efficient ethylene polymerization at at elevated
temperatures (60–90 °C)
elevated temperatures while
(60–90 retaining
◦ C) high molecular
while retaining weightsweights
high molecular of the resulting PE, asPE,
of the resulting distinct from
as distinct
the
from analogous monofunctional
the analogous monofunctional systems (A3) [37].
systems (A3) [37].

Chart 1. Bis(imino)pyridine cobalt complexes and cycloalkyl ring fused derivatives.

Chart 1. Bis(imino)pyridine cobalt complexes and cycloalkyl ring fused derivatives.
On the other hand, the modification of bis(imino)pyridine backbone to enhance the catalytic
On
propertiestheatother hand,
a higher the modification
temperature. of bis(imino)pyridine
Our group has been interestedbackbone to enhance
in introducing the catalytic
cycloalkyl unit
properties at a higher temperature. Our group has been interested in introducing cycloalkyl
to bis(imino)pyridine ligand sets by adjusting the flexibility of the exterior imine donors to modify unit to
bis(imino)pyridine
the donor properties ligand sets
of the by adjusting
NNN-pincer the flexibility
ligand of the exterior
set and in-turn imine donors
the performance to catalyst
of the modify the
[6].
donor properties of the NNN‐pincer ligand set and in‐turn the performance
With regards to cobalt precatalysts (Chart 1), one [38–42] or two [43–48] cycloalkyl unitof the catalyst [6].fused
With
regards to cobalt
derivatives havingprecatalysts (Chart five
ring sizes between 1), one
and[38–42]
eight areoraccessible
two [43–48]
(seecycloalkyl
for exampleunit fused
B [39], C derivatives
[40], D [41],
having
E [43,44], F [45], and G [47,48], Chart 1). In terms of catalytic performance and the polymericD
ring sizes between five and eight are accessible (see for example B [39], C [40], [41], E
products
[43,44], F [45], and G [47,48], Chart 1). In terms of catalytic performance and the polymeric products
Molecules 2019, 24, x 3 of 20
Molecules 2019, 24, 1176 3 of 20

properties, we have observed significant differences between cobalt catalysts (B–G). For example,
five‐membered ring fused bis(imino)pyridine cobalt precatalyst [38], showed lower activities (2.89 ×
properties, we have observed significant differences between cobalt catalysts (B–G). For example,
104 g of PE mol−1(Co) h−1) than their analogues of A and B–G [6]; while using B that containing
five-membered ring fused bis(imino)pyridine cobalt precatalyst [38], showed lower activities (2.89 ×
slightly larger six‐membered ring (Chart 1) [39], results in much higher activities (up to 1.08 × 107 g of
104 g of PE mol−1 (Co) h−1 ) than their analogues of A and B–G [6]; while using B that containing slightly
PE mol−1 (Co) h−1) and better thermal stability than A and C [4,6,39,40], and produces polyethylene
larger six-membered ring (Chart 1) [39], results in much higher activities (up to 1.08 × 107 g of PE mol−1
wax with narrower molecular weight distribution. Expanding the ring size to seven (D and E, Chart
(Co) h−1 ) and better thermal stability than A and C [4,6,39,40], and produces polyethylene wax with
1) [41,43,44], the more flexible structure, leads to increased molecular weight (Mw up to 54.0 kg
narrower molecular weight distribution. Expanding the ring size to seven (D and E, Chart 1) [41,43,44],
mol−1) which is most apparent with doubly‐fused E containing ortho‐cycloalkyl substituent, but E
the more flexible structure, leads to increased molecular weight (Mw up to 54.0 kg mol−1 ) which is
display slightly lower activity their counterparts D. Beyond this, it was found that cyclohexyl fused
most apparent with doubly-fused E containing ortho-cycloalkyl substituent, but E display slightly
pyridine cobalt complexes (B and C) produced the polyethylene with very low molecular weight
lower activity their counterparts D. Beyond this, it was found that cyclohexyl fused pyridine cobalt
(0.82 kg mol−1) and linear saturated structure. The seven‐membered ring fused
complexes (B and C) produced the polyethylene with very low molecular weight (0.82 kg mol−1 )
pyridine(imino)cobalt precatalyst (D and E) produced the higher molecular weight polyethylene
and linear saturated structure. The seven-membered ring fused pyridine(imino)cobalt precatalyst
(3.2 kg mol−1) that contained the vinyl group, which has a significant potential application in the
(D and E) produced the higher molecular weight polyethylene (3.2 kg mol−1 ) that contained the vinyl
polywax in the package field [6]. The other interesting is the one cycloalkyl fused pyridine (imino)
group, which has a significant potential application in the polywax in the package field [6]. The other
cobalt (B and D) showed better thermal stability (optimum temperature: 50~60 °C) and higher
interesting is the one cycloalkyl fused pyridine (imino) cobalt (B and D) showed better thermal stability
activity (8.65–10.09 × 106 g of PE mol−1(Co) h−1) than that by double cyclcoalkyl fused
(optimum temperature: 50~60 ◦ C) and higher activity (8.65–10.09 × 106 g of PE mol−1 (Co) h−1 ) than
bis(imino)pyridine cobalt complexes (C, E, F, and G) (activity: 2.89–5.04 ×106 g of PE mol−1(Co) h−1
that by double cyclcoalkyl fused bis(imino)pyridine cobalt complexes (C, E, F, and G) (activity:
and optimum temperature at 30–40 °C). Very recently, we have reported a series of E derivatives
2.89–5.04 × 106 g of PE mol−1 (Co) h−1 and optimum temperature at 30–40 ◦ C). Very recently, we have
that incorporate the cycloalkyl substitution on the ortho position of N‐aryl group, which exhibited
reported a series of E derivatives that incorporate the cycloalkyl substitution on the ortho position of
good activity (2.0 × 106 g of PE mol−1(Co) h−1) with6 the optimum temperature of 30 °C [43].
N-aryl group, which exhibited good activity (2.0 × 10 g of PE mol−1 (Co) h−1 ) with the optimum
Considering the potential positive effect by the cycloalkyl substituent on the ortho position of N‐aryl
temperature of 30 ◦ C [43]. Considering the potential positive effect by the cycloalkyl substituent on
group and the backbone of monocycloheptyl fused pyridine(imino) on the thermal stability and
the ortho position of N-aryl group and the backbone of monocycloheptyl fused pyridine(imino) on the
polymerization activity toward ethylene polymerization, therefore, in this work we focused on the
thermal stability and polymerization activity toward ethylene polymerization, therefore, in this work
mono cycloheptyl‐fused bis(imino)pyridine cobalt complexes that incorporated the different ring
we focused on the mono cycloheptyl-fused bis(imino)pyridine cobalt complexes that incorporated
size of cycloalkyl on the ortho position of N‐aryl group and their catalytic behavior toward ethylene
the different ring size of cycloalkyl on the ortho position of N-aryl group and their catalytic behavior
polymerization in detail.
toward ethylene polymerization in detail.

2. Results
2. Results

2.1. Synthesis and Characterization of Ligands and Cobalt Complexes Co1–Co6

According to a literature literature procedure

procedure [49],
[49], the condensation reactions of
2‐acetyl‐5,6,7,8‐tetrahydrocycloheptapyridin‐9‐onewithwith
2-acetyl-5,6,7,8-tetrahydrocycloheptapyridin-9-one 2‐cycloalkylaniline
2-cycloalkylaniline hydrochloride
hydrochloride derivatives
derivatives
were wereinconducted
conducted in n-butanol
the refluxing the refluxing n‐butanol
to form to form
the desired the desired
NNN-pincer NNN‐pincer
ligands ligands
(L1/L1’–L6/L6’,
(L1/L1’–L6/L6’, Chart 1) in moderate isolated yield (32%–39%,
Chart 1) in moderate isolated yield (32%–39%, Scheme 1). Scheme 1).

ArNH3Cl-
N n-butanol N N
O N N HN
O N Ar
1 Ar Ar Ar
R L1- L6 L1'- L6'

Ar: R2
CoCl2 EtOH L' : L = 0.09 ~ 0.28

L1 L2 L3 L4 L5 L6
Co1 Co2 Co3 Co4 Co5 Co6 N
1 C5H9 C6H11 C8H15 C5H9 C6H11 C8H15 Ar N N
R Co Ar
2 Cl
R H H H Me Me Me Cl

Scheme 1.
Scheme Synthetic route
1. Synthetic route of
of ligands L1–L6 and
ligands L1–L6 and cobalt
cobalt complexes
complexes Co1–Co6.
Co1–Co6.

The 11 H-NMR spectra of the ligands indicated two isomers for each because of the migration
The H‐NMR spectra of the ligands indicated two isomers for each because of the migration of
of double bond to the imino group linked to the cycloheptane, illustrating major compounds with
double bond to the imino group linked to the cycloheptane, illustrating major compounds with the
the remaining imino group (L) instead of double bonds within cycloheptanic derivatives (L0 , minor),
remaining imino group (L) instead of double bonds within cycloheptanic derivatives (L′, minor),
Molecules 2019, 24, x 4 of 20

Molecules 2019, 24, 1176 4 of 20

which is similar to our previous work [49,50]. The isomers with N–H groups are confirmed with the
observation range from 3372 to 3379 cm−1 in their IR spectra, while the isomers containing the C=N
groups
whichwere observed
is similar to ourcharacteristic
previous work band around
[49,50]. The1644
isomers cm−1with
. ThenN–H using
groupsthe are
literature
confirmedprocedure
with the
[40,49], the corresponding
observation range from 3372 NNN‐pincer
to 3379 cm −1
ligands (L1/L1’–L6/L6)
in their IR spectra, reacted
while the with cobalt(II)
isomers dichloride
containing the C=Nin
ethanol
groupsto weregive the corresponding
observed characteristic band − 1
2‐(1‐arylimino)ethyl‐9‐arylimino‐5,6,7,8‐tetrahydrocyclohepta
around 1644 cm . Then using the literature procedure [40,49],
‐pyridine‐cobalt(II) chloride complexes,
the corresponding NNN-pincer [2‐(1‐ArN)C2Hreacted
ligands (L1/L1’–L6/L6) 3‐9‐ArN‐5,6,7,8‐C 5H8C
with cobalt(II) 5H3N]CoCl
dichloride in2,ethanol
(Ar = to
2‐(C 5Hthe
give 9)‐6‐MeC 6H3 Co1, 2-(1-arylimino)ethyl-9-arylimino-5,6,7,8-tetrahydrocyclohepta
corresponding 2‐(C6H11)‐6‐MeC6H3 Co2, 2‐(C8H15)‐6‐MeC6H3 Co3, 2‐(C5H 9)‐4,6‐Me2C6H2
-pyridine-cobalt(II)
Co4, 2‐(C6H
chloride 11)‐4,6‐Me2[2-(1-ArN)C
complexes, C6H2 Co5, and 2‐(C8H15)‐4,6‐Me
2 H3 -9-ArN-5,6,7,8-C 5H2C86CH52HCo6),
3 N]CoClin 2high
, (Ar yields
= 2-(C5(91–96%).
H9 )-6-MeCAll 6 H3theCo1,
ligands
2-(C6 HL1–L6
11 have
)-6-MeC Hbeen
6 3 Co2, characterized
2-(C H
8 15 by
)-6-MeC FT‐IR,
H
6 3
1H/13C‐NMR spectroscopy and elemental analysis.
Co3, 2-(C H
5 9 )-4,6-Me C
2 6 2H Co4, 2-(C H
6 11 )-4,6-Me 2 6 H2
C
TheCo5, and 2-(C8 H15 )-4,6-Me2 C6 H2 Co6), in high yields (91–96%). All the ligands L1–L6 have the
cobalt complexes Co1–Co6 have been characterized by IR and elemental analysis and been
structure of Co2byand
characterized Co31 H/
FT-IR, was13 C-NMR
confirmed by single‐crystal
spectroscopy X‐ray diffraction.
and elemental analysis. The Comparing the IR
cobalt complexes
spectra
Co1–Co6 of freehaveligands
been with their corresponding
characterized Co complexes,
by IR and elemental there
analysis is no
and theabsorption
structure of related
Co2 and to the
Co3
N–Hwasgroups;
confirmed moreover, the adsorption
by single-crystal X-ray around 1644 cm
diffraction. −1 for νC=N in
Comparing theligand compounds
IR spectra of freeisligands
shiftedwithto
lower
theirwavenumber
corresponding around 1609 cm−1 within
Co complexes, there isthenocobalt complexes
absorption indicating
related to the N–Heffective coordination
groups; moreover,
of the
Co–N sp2 [40,41].around 1644 cm−1 for νC=N in ligand compounds is shifted to lower wavenumber
adsorption
around 1609 cm−1 within the cobalt complexes indicating effective coordination of Co–Nsp2 [40,41].
2.2. Single‐Crystal X‐ray Diffraction Study
2.2. Single-Crystal X-ray Diffraction Study
The single‐crystals of Co2 and Co3 suitable for the X‐ray determinations were obtained by slow
diffusionTheofsingle-crystals
n‐hexane intoof their
Co2solution
and Co3insuitable
dichloromethane
for the X-ray at determinations
room temperature. wereTheir molecular
obtained by slow
structures
diffusionare of shown
n-hexanein Figure 1a,b,
into their and selected
solution bond lengths and
in dichloromethane angles
at room in Table 1. Their molecular
temperature.
structures are shown in Figure 1a,b, and selected bond lengths and angles in Table 1.

(a) (b)
Figure
Figure1. 1.ORTEP
ORTEPdrawing
drawingofofCo2 (a) and
Co2(a) Co3(b)
and Co3 (b)with
withthermal
thermalellipsoids
ellipsoids
at at
thethe
30%30% probability
probability level.
level. Hydrogen
Hydrogen atoms
atoms are omitted
are omitted for clarity.
for clarity.

Selected bond lengths ◦ ) for Co2 and Co3.

Table
Table 1. 1.
Selected bond lengths (Å)(Å) and
and angles
angles (°)( for Co2 and Co3.
Co2 Co3 Co2 Co3
Co2 Co3 Co2 Co3
Bond Lengths (Å)
Co(1)–N(1) 2.203(4) Bond Lengths
2.193(4) (Å)
Co(1)–N(2) 2.063(4) 2.043(4)
Co(1)−N(1)
Co(1)–N(3) 2.203(4)
2.182(3) 2.193(4)
2.175(4) Co(1)−N(2)
Co(1)–Cl(1) 2.063(4)
2.2922(13) 2.043(4)
2.3062(15)
Co(1)–Cl(2)
Co(1)−N(3) 2.2646(12)
2.182(3) 2.2478(14)
2.175(4) N(1)–C(2)
Co(1)−Cl(1) 1.286(6)
2.2922(13) 1.296(6)
2.3062(15)
N(3)–C(11) 1.286(5) 1.296(6)
Co(1)−Cl(2) 2.2646(12) 2.2478(14) N(1)–C(2) 1.286(6) 1.296(6)
Bond Angles (deg)
N(3)–C(11)
N(1)–Co(1)–N(2)
1.286(5)
73.80(14)
1.296(6)
74.91(16) N(1)–Co(1)–N(3) 142.70(13) 147.01(15)
N(2)–Co(1)–N(3) 74.65(14) Bond AnglesN(1)–Co(1)–Cl(2)
75.80(16) (deg) 97.55(11) 98.74(11)
N(2)–Co(1)–Cl(2) 73.80(14)
N(1)−Co(1)−N(2) 152.75(11) 151.03(13) N(1)−Co(1)−N(3)
74.91(16) N(3)–Co(1)–Cl(2) 101.45(10)
142.70(13) 99.53(11)
147.01(15)
N(1)–Co(1)–Cl(1) 74.65(14)
N(2)−Co(1)−N(3) 100.12(11) 98.37(11) N(1)−Co(1)−Cl(2)
75.80(16) N(2)–Co(1)–Cl(1) 95.66(11)
97.55(11) 89.97(12)
98.74(11)
N(3)–Co(1)–Cl(1) 102.30(10) 96.45(12) Cl(2)–Co(1)–Cl(1) 111.42(5) 119.00(6)
N(2)−Co(1)−Cl(2)
C(11)–N(3)–Co(1)
152.75(11)
116.0(3)
151.03(13)
113.9(3)
N(3)−Co(1)−Cl(2)
C(2)–N(1)–Co(1)
101.45(10)
114.9(3)
99.53(11)
114.8(4)
N(1)−Co(1)−Cl(1) 100.12(11) 98.37(11) N(2)−Co(1)−Cl(1) 95.66(11) 89.97(12)
N(3)−Co(1)−Cl(1) 102.30(10) 96.45(12) Cl(2)−Co(1)−Cl(1) 111.42(5) 119.00(6)
C(11)–N(3)–Co(1) 116.0(3) 113.9(3) C(2)–N(1)–Co(1) 114.9(3) 114.8(4)
Molecules 2019, 24, 1176 5 of 20

Co2 and Co3 have a similar structure and each cobalt was surrounded by two chlorides and
three nitrogen atoms belonging to the corresponding NNN-pincer ligand. Both of them possessed
distorted square-pyramidal geometry, in which three nitrogen atoms N1, N2, N3 and Cl1 formed the
base plane and Cl2 occupying the apical position. The cobalt atom lies at a distance of 0.505 Å above
the basal plane for Co2 and 0.447 Å for Co3 in a manner similar to that observed in related NNNCoCl2
counterparts [40,41,45,47]. In these two structures, the bond length of Co-Npy [2.063(4) Å (Co2), 2.043(1)
Å (Co3)] is significantly shorter than that of Co-Nimine [2.203(4) and 2.183(3) Å (Co2), 2.193(4) and
2.175(4)Å (Co3)], suggesting the stronger donor ability by N-py. At the same time, they are close to that
in A (2.051(3) Å) [4], B (2.040(3) Å) [39], D (2.036(4)–2.052(5) Å) [40,41], but are shorter than that of E
(2.087(4) Å) [44]. By contrast, the bond length of Co–Nimine [2.175(4)–2.203(4) Å] are longer than that in
E (2.128(3) and 2.176(3) Å) [51] and α,α0 -bis(arylimino)-2,3:5,6-bis(hexamethylene)pyridine-cobalt(II)
complexes (range: 2.1180(18) - 2.1633(18) Å) [47], similar to those A [4], B [39], and D [40,41] (range:
2.193–2.320 Å, Chart 1), highlighting the good chelation properties of D to the cobalt center. The N-aryl
rings are almost perpendicular to the coordination plane with dihedral angles of (74.23◦ and 78.48◦ )
for Co2 and (83.84◦ and 71.39◦ ) for Co3, respectively. Concurrently, the cyclo-substituents always
located in trans-position. The torsion angles for N(1)–C(2)–C(3)–N(2) [2.09◦ (Co2), −7.08◦ (Co3)]
and N(3)–C(11)–C(12)–N(2) [−10.57◦ (Co2), 13.35◦ (Co3)] highlight the deviation from co-planarity
between the pyridine ring and the neighboring imine vectors, and the large distinct torsion angles are
attributed to the unsymmetrical framework and the different sizes ortho-cycloalkyl substituent [44].
The interesting is the substituents on the ortho position of N-aryl group are always in trans-position.

2.3. Ethylene Polymerization

Based on previous findings for structurally related cobalt (II) chloride complexes (e.g., B–E in
Chart 1) [39–47], the highest catalytic activity for ethylene polymerization tends to be achieved upon
activation with either methylaluminoxane (MAO) or modified methylaluminoxane (MMAO) [6–15].
Therefore, these two co-catalysts were employed to investigate the ethylene polymerization in detail
as follows.

2.3.1. Ethylene Polymerization using Co2/MAO

With MAO as co-catalyst, Co2 was employed as precatalyst to investigate the ethylene
polymerization systematically at various parameters, such as different Al/Co molar ratios, reaction
temperatures and run times and polymerization results are collected in Table 2.
First of all, with the ethylene pressure set at 10 atm and the Al/Co ratio fixed at 1000, ethylene
polymerizations were conducted at a different temperature from 30 to 70 ◦ C (runs 1–5, Table 2).
The maximum activity of 2.89 × 106 g of PE mol−1 (Co) h−1 was found at 50 ◦ C affording a
polymeric product; no trace of oligomers could be detected. Further, higher temperature led to
the dramatically decreasing of the polymerization activity (Figure 2a). Meanwhile, the molecular
weight (Mw ) of the polymer was found to decrease from 22.97 kg mol−1 to 6.56 kg mol−1 when
increasing the temperature from 30 ◦ C to 70 ◦ C, which can be ascribed to either the more facile chain
transfer or chain termination with respect to the chain propagation yielding lower molecular weight
PE [4,40,41,45,51–53]. Moreover, their GPC curves showed the unimodal distribution and the resultant
polyethylene possessed narrow polydispersity (PDI = 2.0~3.8), which is consistent with the characters
of single-site active species [6,39–45].
Fixing the temperature at 50 ◦ C, ethylene polymerizations by Co2/MAO were conducted at a different
Al/Co molar ratio from 500 to 3500 (runs 3 and 6–11, Table 2). The highest activity was observed as 3.57
× 106 g of PE mol−1 (Co) h−1 with a molar ratio of 2500 (run 9, Table 2), a lower or higher ratio of
co-catalyst led to lower activities. The molecular weight of the polymer (Mw ) gradually decreased from
14.2 kg mol−1 to 9.39 kg mol−1 , and the molecular weight distribution kept very narrow (PDI = 2.4 −
2.7). This result can be ascribed to increased chain transfer to aluminum occurring as a consequence of the
larger amounts of alkyl aluminum reagent employed [4,40,41,44,51,52]. To our surprise with the Al/Co
Molecules 2019, 24, x 6 of 20

[4,40,41,44,51,52]. To our surprise with the Al/Co molar ratios changing between 3000 and 3500, a
dramatic increase of molecular weight was observed and up to 13.96 kg mol−1 with 3500 equivalents
of MAO2019,
Molecules (Figure 2 (b)). It would seem plausible that the formation of new active species has been
24, 1176 6 of 20
influenced within this molar ratio window, a similar observation has been noted elsewhere [38,44].
On the other hand, with regards to the molecular weight distribution, the PDI of polymers are falling
molar ratios changing between 3000 and 3500, a dramatic increase of molecular weight was observed
in the range from 2.4 to − 3.0, slightly broader than their counterparts D containing symmetric para‐R1
and up to 13.96 kg mol 1 with 3500 equivalents of MAO (Figure 2b). It would seem plausible that
groups (PDI = 2.2) [41], this observation was similar to complex E incorporating α,
the formation of new active species has been influenced within this molar ratio window, a similar
α′‐bis(arylimino)‐2,3:5,6‐bis(hexamethylene)pyridine containing cycloalkyl ortho‐substituents
observation has been noted elsewhere [38,44]. On the other hand, with regards to the molecular weight
[43,44].
distribution, the PDI of polymers are falling in the range from 2.4 to 3.0, slightly broader than their
1 groups (PDI = 2.2) [41], this observation was similar to
counterparts D containing 2. Ethylenepara-R
Tablesymmetric polymerization results using Co2/ MAO a.
0
complex E incorporating α, α -bis(arylimino)-2,3:5,6-bis(hexamethylene)pyridine containing cycloalkyl
Run Precat.
ortho-substituents [43,44].Al/Co T(°C) t(min) PE(g) Act.
b Mw c Mw/Mn c Tm(oC) d
1 Co2 1000 30 30 3.66 2.44 22.97 3.7 133.7
Table 2. Ethylene polymerization results using Co2/ MAO a
2 Co2 1000 40 30 3.74 2.49 17.94 3.8. 131.4
3 Co2 1000 ◦ 50 30 4.33 2.89 b 14.21 c 3.0 131.1
Run Precat. Al/Co T ( C) t (min) PE (g) Act. Mw M w /M n c T m (o C) d
4 Co2 1000 60 30 2.70 1.80 9.37 2.0 130.2
1
5 Co2 Co2 10001000 30 70 30
30 3.66
1.45 2.44
0.96 22.97
6.56 2.53.7 130.1133.7
2 Co2 1000 40 30 3.74 2.49 17.94 3.8 131.4
3 6 Co2 Co2 1000500 50 50 30
30 Trace
4.33 ‐
2.89 ‐
14.21 ‐ 3.0 ‐ 131.1
4 7 Co2 Co2 10001500 60 50 30
30 4.37
2.70 2.91
1.80 9.76
9.37 2.42.0 130.3130.2
5 8 Co2 Co2 10002000 70 50 30
30 1.45
4.43 0.96
2.95 6.56
9.75 2.42.5 130.7130.1
6 9 Co2 Co2 5002500 50 50 30
30 Trace
5.36 3.57- 9.39- 2.7 - 130.0 -
7 Co2 1500 50 30 4.37 2.91 9.76 2.4 130.3
8
10 Co2 Co2 20003000 50 50 30
30
5.10
4.43
3.40
2.95
10.67
9.75
2.62.4 130.5130.7
9 11 Co2 Co2 25003500 50 50 30
30 1.94
5.36 1.29
3.57 13.96
9.39 2.52.7 130.6130.0
10 12 Co2 Co2 30002500 50 50 305 2.03
5.10 8.12
3.40 10.65
10.67 2.62.6 130.3130.5
11 13 Co2 Co2 35002500 50 50 30
15 1.94
4.70 1.29 10.34
6.26 13.96 2.52.5 130.7130.6
12
14 Co2 Co2 25002500 50 50 5
45 2.03
6.28 8.12
2.78 10.65
11.21 2.62.6 131.5130.3
13 Co2 2500 50 15 4.70 6.26 10.34 2.5 130.7
14 15 Co2 Co2 25002500 50 50 60
45 7.44
6.28 2.48
2.78 11.26
11.21 2.72.6 130.1131.5
15 16 e Co2 Co2 25002500 50 50 30
60 4.28
7.44 2.85
2.48 13.04
11.26 2.72.7 130.8130.1
16 e 17 Co2 Co1 25002500 50 50 30
30 4.28
6.13 2.85 10.34
4.09 13.04 2.42.7 130.4130.8
17 18 Co1 Co3 25002500 50 50 30
30 6.13
4.95 4.09 20.20
3.30 10.34 3.92.4 132.4130.4
18 Co3 2500 50 30 4.95 3.30 20.20 3.9 132.4
19
19 Co4 Co4 25002500 50 50 30
30
5.25
5.25
3.50
3.50
13.40
13.40
2.42.4 131.6131.6
20 20 Co5 Co5 25002500 50 50 30
30 4.87
4.87 3.25
3.25 9.78
9.78 2.42.4 130.2130.2
21 21 Co6 Co6 25002500 50 50 30
30 4.82
4.82 3.21
3.21 25.96
25.96 4.44.4 132.8132.8
aa
Reaction conditions:
Reaction conditions: 3 μmol
3 µmol cobalt
cobalt complexes,
complexes, 100 mL100 mL toluene,
toluene, 10 atm C210 ; b Values
H4atm C2H4in
; bunits
Values 6 gunits
of 10in of PEof 10−61
mol
(Co) h −1 ; c Determined using GPC, M : kg mol−1 ; d Determined using DSC; e 5 atm C H .
−1 −1 c w
g of PE mol (Co) h ; Determined using GPC, Mw: kg mol ; Determined using DSC; 5 atm C2H4.
−1 d 2 4 e

(a) (b)
Figure
Figure 2.2. (a)
(a) GPC
GPC curves
curves ofof polyethylene
polyethylene obtained
obtained by
by Co2/MAO
Co2/MAOatatvarious
varioustemperature
temperature(runs
(runs1–5,
1–5,
Table 2); (b)
Table 2); (b)GPC
GPCcurves
curvesof of polyethylene
polyethylene obtained
obtained using
using Co2/MAO
Co2/MAO withwith different
different molarmolar ratio
ratio of of
Al/Co
Al/Co
(runs 3(runs 3 and Table
and 6–11, 6–11, 2).
Table 2).

To the end, the lifetime of the Co2/MAO catalyst was probed by conducting the polymerization
over 5, 15, 30, 45 and 60 min (runs 9 and 12–15, Table 2). Polymerization activity gradually decreased
from 8.12 × 106 g of PE mol−1 (Co) h−1 to 2.48 × 106 g of PE mol−1 (Co) h−1 with prolonging the
Molecules 2019, 24, x 7 of 20

To the end, the lifetime of the Co2/MAO catalyst was probed by conducting the polymerization
over 5, 15, 30, 45 and 60 min (runs 9 and 12–15, Table 2). Polymerization activity gradually decreased
Molecules 2019, 24, 1176 7 of 20
from 8.12 × 106 g of PE mol−1(Co) h−1 to 2.48 × 106 g of PE mol–1 (Co) h–1 with prolonging the reaction
time from, 5 to 60 min, which can be explained by the rapid formation of active species after the
reaction of
addition time
MAO from,
and5 gradual
to 60 min, which canover
deactivation be explained
extended by the rapid
reaction timeformation
[34,40–45].ofItactive species
is indicated
after the addition of MAO and gradual deactivation over extended
that a short time frame was required to generate all active species, and then the onset of partial reaction time [34,40–45]. It is
indicated that
deactivation of aactive
short species
time frame was required
occurred over thetocoursegenerate all active
of the reaction species, and then theethylene
[34]. Decreasing onset of
partial deactivation
pressure to 5 atm, the of polymerization
active species occurred
activityover(2.85the
× 10course
6 g of ofPEthemol reaction
−1 (Co) [34].
h−1) isDecreasing
much lower ethylene
than
pressure to 5 atm, the polymerization activity (2.85 × 10 6 g of PE mol−1 (Co) h−1 ) is much lower than
that (3.57 × 10 g of PE mol (Co) h ) at 10 atm (runs 9 and 16, Table 2), but the resultant PE polymer
6 −1 −1

that (3.57 ×
possessed 106 ghigher
much mol−1 (Co)weight
of PE molecular h−1 ) at(13.04
10 atmvs. (runs
9.399kg and 16,−1Table
mol ). 2), but the resultant PE polymer
possessed much higher molecular weight (13.04 vs. 9.39 kg mol −1 ).
In order to explore the effect imparted by the cycloalkyl ortho‐substitution pattern on
In orderand
performance to explore
polymer the properties,
effect imparted the by
other complexesortho-substitution
the cycloalkyl were additionally pattern on performance
screened using the
and polymer
optimized properties,
reaction the other
conditions complexes independently
established were additionally forscreened
Co2/MAO usingandthe optimized
the resultsreaction
were
conditions established independently for Co2/MAO and the
collected in Table 2 (runs 17–21). On activation with MAO, all the cobalt complexes Co1–Co6 results were collected in Table 2 (runs
17–21). On
displayed activation
good activitieswith MAO,
in the rangeall of
the3.21–4.09
cobalt complexes
× 10 g of PE
6 Co1–Co6
mol (Co)
−1 displayed
h , which
−1 good activities
fall in the
in the order:
range 3.21–4.09 × 10 6 g of 1PE mol−1 (Co) h−1 , which [R1 = cyclopentyl]
Co1 [R1of= cyclopentyl] > Co2 [R = cyclohexyl] > Co3 [R1 = cyclooctyl], fall in the order:
Co4 [RCo1 1=cyclopentyl] > Co5 [R1>
=Co2 [R1 = cyclohexyl]
cyclohexyl] Co3 [R1 = cyclooctyl],
> Co6 [R1 => cyclooctyl] (Figure 3 (a)). Co4 [R1 =cyclopentyl]
These findings indicate > Co5 that 1 = cyclohexyl] > Co6
[Rthe size of cycloalkyl
1
[R = cyclooctyl] (Figure 3a). ofThese findings ortho
group on the ortho position N‐aryl groupindicate
affects thatthe the size ofactivity,
catalytic cycloalkyl group on
in which lessthe
bulky
position of N-aryl group affects the catalytic activity, in which
cyclopentyl systems gave the higher activities (Co1, Co4) and the bulkiest group of cyclooctylless bulky cyclopentyl systems gave
the higher
showed the activities
lowest (Co3, (Co1, Co4)
Co6) and theAll
activities. bulkiest group of
the resultant PEcyclooctyl
by different showed
cobalt the lowest (Co3,
complexes Co1–Co6 Co6)
activities. narrow
possessed All the resultant
distribution PE by
and different
PDI value cobalt complexes
ranged from 2.4 to 3.9,possessed
Co1–Co6 a slightly narrow
broaderdistribution
than that
and PDI
found in thevalue
D/MAO ranged from The
system. 2.4 to 3.9,traces
GPC a slightly broader
clearly showed than that found
unimodal in the D/MAO
distribution (Figure 3). system.
But
Thepolymer
the GPC traces by clearly
Co3 and showed unimodal
Co6 that bear thedistribution
bulkiest (Figure 3). But the polymer
ortho‐substituent by Co3
of cyclooctyl and Co6 the
possessed that
bear the
highest bulkiest ortho-substituent
molecular weight among their of cyclooctyl
analogues,possessed
the similar thetrends
highest weremolecular weight for
also observed amongE/MAO their
analogues,
system [44].theThesimilar trends were
para‐methyl also observed
substituted complexes for E/MAO
Co4–Co6 system
showed The para-methyl
[44].slightly substituted
lower activity than
complexes Co4–Co6
unsubstituted showedwhich
ones Co1–Co3, slightlywas lower activity than
demonstrated by theunsubstituted
activity order: ones
Co1 (R2 = H) >which
Co1–Co3, Co4 (Rwas 2=

demonstrated by the activity order: Co1 (R 2 = 2H) > Co4 (R2 =2 Me), Co2 (R2 = H) > Co5 (R2 = Me) and
Me), Co2 (R = H) > Co5 (R = Me) and Co3 (R = H) > Co6 (R = Me). However, Figure 3 shows that
2 2

Co3 (R2 = weights

molecular H) > Co6by (R2Co1–Co3
= Me). However,
are lower Figure
than3 shows
that by that molecular
Co4–Co6 weights by Co1–Co3
respectively. These trends are lower
are
than that
similar by Co4–Co6
to their respectively.
analog complex These trends are similar to their analog complex of B [39].
of B [39].

(a) (b)

Figure
Figure3.3.(a)
(a)Polymerization
Polymerizationactivity
activityand
and MMwwofofPEPEby
byCo1‐Co6/MAO;
Co1-Co6/MAO;(b)
(b)GPC
GPCcurves
curvesofofPE
PEobtained
obtained
by
byCo1‐Co6/MAO
Co1-Co6/MAO (runs 9 and
(runs 17–21,
9 and 17–21,Table
Table2).2).

InIncomparison
comparisonwith with previously
previously reportedreported
cobaltcobalt precatalysts,
precatalysts, such assuch
A, B as and 2)D
andA,D B(Chart
(Chart 2) [4,39–41,44], the current systems, Co1–Co6, under comparable polymerization
[4,39–41,44], the current systems, Co1–Co6, under comparable polymerization conditions (namely conditions
(namely
MAO MAO as co-catalyst,
as co‐catalyst, 10 atm C2H410 , 30atm
min)Cexhibited
2 H4 , 30 min) exhibited
relatively lowerrelatively lower catalytic
catalytic activity (3.21–4.09activity
× 106
6 − 1 − 1
of PE mol×−1 10
g(3.21–4.09 (Co)g hof PEbut
−1), mol (Co) h than
are higher ), but arebyhigher
that than that
precatalyst by precatalyst
E (Chart 2). On theE (Chart 2). Onthe
other hand, the
other hand, the resulting polymers by Co1–Co5/MAO possessed much
resulting polymers by Co1–Co5/MAO possessed much higher molecular weight than that found inhigher molecular weight
than thatThese
D/MAO. foundfindings
in D/MAO. These
heights cycloalkyl heights cycloalkylinortho-substituents
findingsortho‐substituents the N‐aryl groupinfavored
the N-aryl
the group
high
favored the
molecular high molecular
weight weight polymer formation.
polymer formation.
Molecules 2019, 24, 1176 8 of 20
Molecules 2019, 24, x 8 of 20

Chart
Chart 2. Comparison of
2. Comparison the M
of the Mw , polydispersity (PDI) and polymerization activity of previously
w, polydispersity (PDI) and polymerization activity of previously
reported cobalt precatalysts (A [4],
reported cobalt precatalysts (A [4], BB [39],
[39], D
D [40],
[40], E
E [44]
[44] and
and H
H [38])
[38]) with
with MAO
MAO as
as activator
activator under
under
related condition.
related condition.
2.3.2. Ethylene Polymerization Using Co2/MMAO
2.3.2. Ethylene Polymerization Using Co2/MMAO
Under the optimized molar ratio for Co2/MAO (Al/Co = 2500), ethylene polymerization by
Under the
Co2/MMAO wereoptimized
conductedmolar ratio temperatures
at various for Co2/MAO (Al/Co
(from = to
30 ◦ C 2500), ethylene
60 ◦ C) at 10 atmpolymerization by
ethylene pressure
Co2/MMAO were conducted at various temperatures (from 30 °C to 60 °C) at 10 atm
(runs 1–4, Table 2). The results showed that the highest activity of 2.95 × 10 g of PE mol (Co) h−1
6 − 1 ethylene
pressure (runs 1–4, Table 2). The results showed that the highest activity of 2.95 × 106 g of PE
was also observed at 50 ◦ C (run 3, Table 3), similar to the results by Co2/MAO (2.89 × 106 g of PE
mol–1(Co) h–1 was also observed at 50 °C (run 3, Table 3), similar to the results by Co2/MAO (2.89 ×
mol−1 (Co) h−1 ). Further, higher temperature led to the decrease of activity, indicating the partial
106 g of PE mol–1 (Co) h–1). Further, higher temperature led to the decrease of activity, indicating the
decomposition of the active species [4,40,41,45,51–53]. The molecular weight of PE decreased from
partial decomposition of the active species [4,40,41,45,51–53]. The molecular weight of PE decreased
12.98 kg mol−1 to 6.41kg mol−1 with the increasing the temperature from 30 ◦ C to 60 ◦ C, which can
from 12.98 kg mol−1 to 6.41kg mol−1 with the increasing the temperature from 30 °C to 60 °C, which
be ascribed to either increased chain transfer to aluminum or chain termination by β-H elimination
can be ascribed to either increased chain transfer to aluminum or chain termination by β‐H
at the higher temperature [47–54]. However, all the resultant PE possessed quite narrow distribution
elimination at the higher temperature [47–54]. However, all the resultant PE possessed quite narrow
(PDI = 2.5) and GPC traces showed unimodal distribution, which is a typical character of a single site
distribution (PDI = 2.5) and GPC traces showed unimodal distribution, which is a typical character of
catalyst system. A similar observation was also reported for their counterparts B, D and E (Chart 2).
a single site catalyst system. A similar◦observation was also reported for their counterparts B, D and
With the temperature fixed at 50 C, the influence of the Al/Co molar ratio was investigated in
E (Chart 2).
the range of 1500 to 3000 (runs 3, 5–7, Table 3). A topmost of activity 2.95 × 106 g of PE mol−1 (Co)h−1
With the temperature fixed at 50 °C, the influence of the Al/Co molar ratio was investigated in
was achieved at the molar ratio of 2500, which is similar to the results with MAO. As with MMAO,
the range of 1500 to 3000 (runs 3, 5–7, Table 3). A topmost of activity 2.95 × 106 g of PE mol−1(Co)h−1
the resultant polyethylenes possessed high molecular weights (8.19–10.22 kg mol−1 ) and narrow
was achieved at the molar ratio of 2500, which is similar to the results with MAO. As with MMAO,
polydispersities (Mw /Mn ≈ 2.5), which is consistent with single-site characteristics for the active
the resultant polyethylenes possessed high molecular weights (8.19–10.22 kg mol−1) and narrow
species [40–45].
polydispersities (Mw/Mn ≈ 2.5), which is consistent with single‐site characteristics for the active
In order to investigate the lifetime of the active species, the polymerization tests were conducted
species [40–45].
over different reaction time from 5, 15, 30 and 60 min (runs 3 and 8–10, Table 3). The results showed
In order to investigate the lifetime of the active species, the polymerization tests were
that polymerization activity decreased from 7.04 to 2.07 × 106 g of PE mol−1 (Co) h−1 when increasing
conducted over different reaction time from 5, 15, 30 and 60 min (runs 3 and 8–10, Table 3). The
the time from 5 to 60 min. As with MMAO system, the molecular weights of the resultant polymer are
results showed that polymerization activity decreased from 7.04 to 2.07 × 106 g of PE mol−1 (Co) h−1
falling in the range from 8.19 to 10.49 kg mol−1 , and displaying narrow molecular weight distribution
when increasing the time from 5 to 60 min. As with MMAO system, the molecular weights of the
(Mw /Mn = 2.4–3.0). With the ethylene pressure reduced to 5 atm, the activity (1.90 × 106 g of PE mol−1
resultant polymer are falling in the range from 8.19 to 10.49 kg mol−1, and displaying narrow
(Co) h−1 ) was much lower than that at 10 atm (run 8, Table 3).
molecular weight distribution (Mw/Mn = 2.4–3.0). With the ethylene pressure reduced to 5 atm, the
With MMAO as co-catalyst, all the cobalt complexes Co1–Co6 were evaluated for their ethylene
activity (1.90 × 106 g of PE mol−1 (Co) h−1) was much lower than that at 10 atm (run 8, Table 3).
polymerization and they also displayed good activity (2.24–3.34 × 106 g of PE mol−1 (Co) h−1 ).
With MMAO as co‐catalyst, all the cobalt complexes Co1–Co6 were evaluated for their ethylene
The similar trends in activity and molecular weight as MAO are observed, in which the cyclopentyl
polymerization and they also displayed good activity (2.24–3.34 × 106 g of PE mol−1 (Co) h−1). The
similar trends in activity and molecular weight as MAO are observed, in which the cyclopentyl
substituted Co1 and Co4 displayed the highest activity and cyclooctyl substituted cobalt complex
 Molecules 2019, 24, x 9 of 20
Molecules 2019, 24, 1176 9 of 20

(Co3 and Co6) gave the lowest activity, but produced the highest molecular weight polyethylene
(runs 3, 12–16,
substituted Table
Co1 and Co43). In comparison
displayed with
the highest D/MMAO,
activity the ortho‐cycloalkyl
and cyclooctyl systems
substituted cobalt in general
complex (Co3
exhibited more than twice higher molecular weight, although the catalytic activity of D/MMAO is
and Co6) gave the lowest activity, but produced the highest molecular weight polyethylene (runs 3,
nearly twice as much as that seen for Co1 and Co4, and almost three times that for Co2–Co3 and
12–16, Table 3). In comparison with D/MMAO, the ortho-cycloalkyl systems in general exhibited more
Co5–Co6. In addition, the molecular weights obtained using Co1–Co6 (range: 8.19–15.94 kg mol−1)
than twice higher molecular weight, although the catalytic activity of D/MMAO is nearly twice as
are all significantly higher than that seen for D/MMAO system (2.5 kg mol−1) [40], which also
much as that seen for Co1 and Co4, and almost three times that for Co2–Co3 and Co5–Co6. In addition,
illustrated the steric effect of the ortho cycloalkyl substituents suppressed the chain transfer and led
the molecular weights obtained using Co1–Co6 (range: 8.19–15.94 kg mol−1 ) are all significantly higher
to the high molecular weight of the polymer. As−shown by their GPC curves in Figure 4, the MWD of
than that seen for D/MMAO system (2.5 kg mol 1 ) [40], which also illustrated the steric effect of the
polymeric products are falling in the range 2.4 to 4.4.
ortho cycloalkyl substituents suppressed the chain transfer and led to the high molecular weight of the
polymer. As shown by their GPC curves in Figure 4, the MWD of polymeric products are falling in the
Table 3. Ethylene polymerization results using Co2/ MMAO a.
range 2.4 to 4.4.
Run Precat. Al/Co T(°C) t(min) PE(g) Act. b Mw c Mw/Mn c Tm(oC) d
3. Ethylene a.
1 Co2 Table2500 30polymerization
30 results using
3.34 2.23 Co2/MMAO
12.98 2.8 132.5
2 Co2 2500 ◦ 40 30 3.82 2.55 11.42c 2.6 130.3o d
Run Precat. Al/Co T ( C) t (min) PE (g) Act. b Mw M w /M n c T m ( C)
3 Co2 2500 50 30 4.43 2.95 8.19 2.5 129.1
1 Co2 2500 30 30 3.34 2.23 12.98 2.8 132.5
4 Co2 2500 60 30 3.20 2.13 6.41 2.5 128.1
2 Co2 2500 40 30 3.82 2.55 11.42 2.6 130.3
3 5 Co2 Co2 2500 1500 50 50 3030 3.62 2.95
4.43 2.41 10.22
8.19 2.4
2.5 130.1
129.1
4 6 Co2 Co2 2500 2000 60 50 3030 3.75 2.13
3.20 2.50 9.27
6.41 2.7
2.5 129.4
128.1
5 7 Co2 Co2 1500 3000 50 50 3030 3.62
2.27 2.41 1.51 10.22
9.86 2.4
2.3 130.1
129.9
6 Co2 2000 50 30 3.75 2.50 9.27 2.7 129.4
8 Co2 2500 50 5 1.76 7.04 10.49 2.5 130.0
7 Co2 3000 50 30 2.27 1.51 9.86 2.3 129.9
8 9 Co2 Co2 2500 2500 50 50 5 15 3.98
1.76 5.31
7.04 8.29
10.49 2.5
2.5 129.1
130.0
9 10 Co2 Co2 2500 2500 50 50 1560 6.21 5.31
3.98 2.07 10.06
8.29 2.4
2.5 131.2
129.1
10 11 e Co2 Co2 2500 2500 50 50 6030 6.21
2.85 2.07 1.90 10.06
8.90 2.4
2.5 131.2
129.9
11 e 12 Co2 Co1 2500 2500 50 50 3030 2.85
5.01 1.90 8.90
3.34 10.01 2.5
2.4 129.9
130.0
12 Co1 2500 50 30 5.01 3.34 10.01 2.4 130.0
13
13 Co3 Co3 2500 2500 50 50 30
30 3.74 2.49
3.74
2.49 14.72
14.72
2.2
2.2
130.9
130.9
14 14 Co4 Co4 2500 2500 50 50 3030 4.87 3.25
4.87 3.25 10.79
10.79 2.4
2.4 129.8
129.8
15 15 Co5 Co5 2500 2500 50 50 3030 3.98 2.65
3.98 2.65 9.22
9.22 2.6
2.6 129.6
129.6
16 16 Co6 Co6 2500 2500 50 50 3030 3.36
3.36 2.24 15.94
2.24 15.94 4.5
4.5 133.3
133.3
a aReaction conditions: 3 µmol cobalt complexes, 100 mL toluene, 10 atm C H ; b Values in units of 106 in
g of PE mol −1
Reaction conditions: 3 μmol cobalt complexes, 100 mL toluene, 2 10
4 atm C2H4; b Values units of 106
(Co) h−1 ; c Determined using GPC, M w : kg mol −1 ; d Determined using DSC; e 5 atm C H .
2 4
g of PE mol (Co) h ; Determined using GPC, Mw: kg mol ; Determined using DSC; 5 atm C2H4.
−1 −1 c −1 d e

(b)
(a)
Figure4. 4.
Figure (a)(a) Polymerization
Polymerization activity
activity and Mand
w ofM w of
PE PE by Co1‐Co6/MMAO;
by Co1-Co6/MMAO; (b) GPC(b) GPCofcurves
curves of PE
PE obtained
obtained
by by Co1–Co6/MMAO
Co1–Co6/MMAO (runs 3 and(runs 3 and
12–16, 12–16,
Table 3). Table 3).

2.4.
2.4.Characterization
CharacterizationofofPolyethylene
Polyethylene
Regardless
RegardlessofofMMAO
MMAOororMAO MAOactivation,
activation,narrow
narrowunimodal
unimodaldistributions
distributionsofofthe
thepolymers
polymersare
are
observed
observed(M(Mww/M =2.2–4.5)
/Mnn=2.2–4.5) consistent
consistent withwith single-site
single‐site active
active species.
species. All
All the Tmthe Tm of
values values of the
the polymer
polymer ◦ to 133 ◦ C [6,40–45]. To provide further support for the linearity of the
ranging ranging
from 129from
°C to129
133 C
°C [6,40–45]. To provide further support for the linearity of the polymers,
polymers, representative PE samples using Co1/MAO ◦ C (run 9, Table 2) were characterized by
representative PE samples using Co1/MAO at 50 at°C50(run 9, Table 2) were characterized by
1H/13C‐NMR spectroscopy at high temperature (recorded in 1,1,2,2‐tetrachloroethane‐d2 at 120 °C,
Molecules 2019, 24, 1176 10 of 20
Molecules 2019, 24, x 10 of 20
Molecules 2019, 24, x 10 of 20
1Figures 5 and
H/13 C-NMR
6). The 1H‐NMR spectra clearly showed the weak downfield multiplets at δ 5.90 and◦ δ
spectroscopy at high temperature (recorded in 1,1,2,2-tetrachloroethane-d2 at 120 C,
5.00, the 5typical
Figures 6).vinylic
and6). signal (Figure
The11H-NMR
H‐NMR spectra5). Whileshowed
clearly the integration
weakratio
the weak for H1:H
downfield 2/H2’:HI is close
multiplets to and
1:2:3,
Figures 5 and The spectra clearly showed the downfield multiplets at
at δδ 5.90
5.90 and δδ
indicating
5.00,the the
thetypical only the
typicalvinylic unsaturated
vinylicsignal
signal(Figure chain
(Figure5). structure
5).While
Whilethe in the PE.
theintegration The
integrationratioshift
ratiofor 114.38
forHH:H and 139.54 in 13C‐NMR
1:H2/H2’:HI is close to 1:2:3,
5.00, 1 2 /H2 ’:HI is close to 1:2:3,
spectra wasthe
indicating ascribed
only thetounsaturated
the unsaturated
chain chain endsin(–CH=CH
structure the PE. 2) [16,40,41,43,45],
The shift 114.38 andwhich
139.54 agreed
in 13
13C‐NMRwell
indicating the only the unsaturated chain structure in the PE. The shift 114.38 and 139.54 in C-NMR
with 1
spectra H‐NMR spectra.to
was ascribed Inthe
addition, the lower
unsaturated chainintensity peaks at 232.24,
ends (–CH=CH 22.92 and 14.22
) [16,40,41,43,45], corresponding
which agreed well
spectra was ascribed to the unsaturated chain ends (–CH=CH2 ) [16,40,41,43,45], which agreed well
to an n‐propyl end‐group further supported the linear structure of the polyethylene
with H‐NMR spectra. In addition, the lower intensity peaks at 32.24, 22.92 and 14.22 corresponding
1 [16,18,45]. These
with 1 H-NMR spectra. In addition, the lower intensity peaks at 32.24, 22.92 and 14.22 corresponding
findings are further evidenced by their high melting temperature (T = 130.0 °C, run
to an n‐propyl end‐group further supported the linear structure of the polyethylene [16,18,45]. These
m 9, Table 2).
to an n-propyl end-group further supported the linear structure of the polyethylene [16,18,45].
findings are further evidenced by their high melting temperature (Tm = 130.0 °C, run 9, Table 2).
These findings are further evidenced by their high melting temperature (Tm = 130.0 ◦ C, run 9, Table 2).

Figure 5. 1H‐NMR spectrum of the polyethylene obtained using Co2/MAO at 50 °C (run 9, Table 2);
Figure 5. 1 H-NMR spectrum of the polyethylene obtained using Co2/MAO at 50 ◦ C (run 9, Table 2);
recorded
Figure 5. in 1,1,2,2‐tetrachloroethane‐d
1H‐NMR 2 at 120 °C. obtained using Co2/MAO at 50 °C (run 9, Table 2);
spectrum of the polyethylene
recorded in 1,1,2,2-tetrachloroethane-d2 at 120 ◦ C.
recorded in 1,1,2,2‐tetrachloroethane‐d2 at 120 °C.

Figure 6. 13 C-NMR spectrum of the polyethylene obtained using Co2/MAO at 50 ◦ C (run 9, Table 2);
Figure 6. 13C‐NMR spectrum of the polyethylene obtained using Co2/MAO at 50 °C (run 9, Table 2);
recorded in 1,1,2,2-tetrachloroethane-d2 at 120 ◦ C.
recorded
Figure 6. in 1,1,2,2‐tetrachloroethane‐d
13C‐NMR 2 at 120 °C. obtained using Co2/MAO at 50 °C (run 9, Table 2);
spectrum of the polyethylene
recorded in 1,1,2,2‐tetrachloroethane‐d2 at 120 °C.
Molecules 2019, 24, x 11 of 20
Molecules 2019, 24, 1176 11 of 20
Molecules 2019, 24, x 11 of 20
The resultant PE by Co2/MMAO were also characterized by 1H/13C‐NMR spectra, and shown in
Figures
The7resultant
The and 8. The
resultant PE H‐NMR
1
Co2/MMAO
by Co2/MMAO spectrum werealsoalso
were showed
also the signal
characterized
characterized by
byof11H/
aH/vinyl group
13 C-NMR
13C‐NMR (δ 5.90and
spectra,
spectra, and
and δshown
5.00),
shown in
which
Figures
in was
Figures also
7 and
7 and confirmed
8. The
8. The 1 1
H‐NMRby
H-NMRthe signal
spectrum in
spectrum
13C‐NMR (δ 139.55, 114.40). However, the integration ratio
also also
showedshowedthe signal of a vinyl
the signal groupgroup
of a vinyl (δ 5.90
(δand
5.90δand
5.00),
δ
for H
which 1:H2/H2’:HI is close to 1:2:5 (Figure
was also confirmed by the signal in 7),
13C‐NMR dissimilar
13 (δ to
139.55, that
114.40). seen
5.00), which was also confirmed by the signal in C-NMR (δ 139.55, 114.40). However, the integration with
However, MAO
the at the
integration same
ratio
temperature,
for Hfor
ratio 1:HH
2/H
which
2’:H I is
suggested
close both
to 1:2:5 the saturated
(Figure and
7), 7), unsaturated
dissimilar to to
that chain
seen structure
with
withMAO in polyethylene.
at
at the same
same
1 :H 2 /H 2 ’:H I is close to 1:2:5 (Figure dissimilar that seen MAO
Moreover, the signal of the lower intensity peaks at 32.24, 22.93 and 14.26
temperature, which suggested both the saturated and unsaturated chain structure in polyethylene.
temperature, in 13C‐NMR corresponds to

n‐propyl
Moreover,
Moreover, end‐group,
the signal of
the indicating
the lowerthe linear structure
intensity
intensity peaks
peaksat of PE.22.93
at32.24,
32.24, These
22.93and
and observations
14.26 wouldcorresponds
13 C-NMR
14.26inin13C‐NMR suggest
correspondsthat,
to
chain termination
n‐propyl
to n-propyl end‐group,
end-group,via β‐H elimination
indicating
indicating the in
thelinear Co2/MMAO
linearstructure system
structureofofPE.PE.Theseis no longer
These observations the
observations would sole chain transfer
would suggest that,
pathway
chain operative,via
chain termination
termination with
via chain
β‐H
β-H transfer to
elimination
elimination inaluminum
in Co2/MMAO
Co2/MMAO nowsystem
competitive
system [16,18,44].
is no longer the sole chain
chain transfer
transfer
pathway operative,
pathway operative, with
with chain
chain transfer
transferto
to aluminum
aluminumnow
nowcompetitive
competitive[16,18,44].
[16,18,44].

Figure 7. 1H‐NMR spectrum of the polyethylene obtained using Co2/MMAO at 50 °C (run 3, Table 3);
1 H-NMR spectrum of the polyethylene obtained using Co2/MMAO at 50 ◦ C (run 3, Table 3);
Figure 7. in
recorded 1,1,2,2‐tetrachloroethane‐d
Figure 7. 1H‐NMR 2 at 120 °C.
spectrum of the polyethylene obtained using Co2/MMAO at 50 °C (run 3, Table 3);
recorded in 1,1,2,2-tetrachloroethane-d2 at 120 ◦ C.
recorded in 1,1,2,2‐tetrachloroethane‐d2 at 120 °C.

Figure 8. 13 C-NMR spectrum of the polyethylene obtained using Co2/MMAO at 50 ◦ C (run 3, Table 3);
Figure
recorded8. in
13C‐NMR spectrum of the polyethylene
1,1,2,2-tetrachloroethane-d2 at 120 ◦ C. obtained using Co2/MMAO at 50 °C (run 3, Table
3); recorded
Figure 8. C‐NMR
13 in 1,1,2,2‐tetrachloroethane‐d 2 at 120 °C.
spectrum of the polyethylene obtained using Co2/MMAO at 50 °C (run 3, Table
3); recorded in 1,1,2,2‐tetrachloroethane‐d2 at 120 °C.
Molecules 2019, 24, 1176 12 of 20

3. Materials and Methods

3.1. General Considerations

All the synthetic procedures for air/moisture-sensitive compounds were performed under a
nitrogen atmosphere with standard Schlenk techniques. Toluene as a solvent for polymerization was
refluxed over sodium (a small amount of benzophenone) and distilled under nitrogen prior to use.
Methylaluminoxane (MAO, 1.46 M solution in toluene) and modified methylaluminoxane (MMAO,
1.93 M in n-heptane) were bought from Akzo Nobel Corp (Nanjing, China). High-purity ethylene
was bought from Beijing Yanshan Petrochemical company (Beijing, China) and used as received.
NMR spectra were recorded using a Bruker DMX 400 MHz instrument (Beijing, China) at ambient
temperature using TMS as an internal standard. FT-IR spectra were recorded using a Perkin-Elmer
System 2000 FT-IR spectrometer (Shanghai, China). Elemental analysis was carried out using a Flash
EA1112 microanalyzer (Beijing, China). Molecular weights and molecular weight distribution of
polyethylenes were determined using a PL-GPC220 GPC/SEC High Temperature System (Beijing,
China). Data collection and handling were carried out using Cirrus GPC Software (Beijing, China) and
Multi Detector Software (Beijing, China). The calibrants for constructing conventional calibration is
Polystyrene Calibration KitS-M-10 from PL Company (Beijing, China). The true average molecular
weights of PE are transferred by inputting the M–H constants of PE. K of 0.727 and α of 40.6 are
provided by PL Company (Beijing, China). Samples were dissolved at a concentration of 1.0 to
2.5 mg mL−1 , depending on the molecular weights. DSC trace and melting points of polyethylene
were obtained from the second scanning run on DSCQ2000 at a heating rate of 10 ◦ C min−1 from
−20 ◦ C to 200 ◦ C. 1 H/13 C-NMR spectra of the polyethylene were recorded using a Bruker DMX
300 MHz instrument (Beijing, China) at 120 ◦ C in deuterated 1,1,2,2-tetrachloroethane with TMS
as an internal standard. The compound of 2-acetyl-5,6,7,8-tetrahydrocycloheptapyridin-9-one was
synthesized according to the literature [49] and the 2-cycloalkylaniline hydrochlorides were prepared
using literature methods [34].

3.2. Synthesis of 2-(1-ArN) C2 H3 -9-ArN-5,6,7,8-C5 H8 C5 H3 N (L1–L6)

Ar = 2-(C5 H9 )-6-MeC6 H3 (L1/L10 ). 2-cyclopentyl-6-methylphenylamine hydrochloride (0.46 g,
2.2 mmol) was added to a solution of (0.20 g, 1.0 mmol,) 2-acetyl-5,6,7,8-tetrahydrocycloheptapyridin-
9-one with p-toluenesulfonic acid (20.0 mg) as catalyst in 30 mL of n-butanol. The mixture was stirred
at reflux temperature for 6h. The solvent was then evaporated at reduced pressure, and the residue was
purified by alumina column chromatography with petroleum ether/dichloromethane/triethylamine
[100/1/1, v/v/v] to afford L1 (0.19 g, 38.1%) as a yellow oil with molar ratio of L1/L10 = 1/0.12
(detected by 1 H-NMR). 1 H-NMR (CDCl3 , 400 MHz, TMS): δ 8.39 (t, J = 7.1 Hz, 1H, L1–HPy ), 8.25 (d,
J = 8.2 Hz, 1H, L10 –HPy ), 7.68 (d, J = 7.8 Hz, 1H, L10 –HPy ), 7.62 (d, J = 8.0 Hz, 1H, L1–HPy ), H), 7.18 (t,
J = 8.5 Hz, 2H, 2 × L1–HAr ), 7.11 (t, J = 5.8 Hz, 2H, 2 × L10 –HAr ), 7.04 (t, J = 6.8 Hz, 2H, 2 × L1–HAr
and 2 × L10 –HAr ), 6.99 (d, J = 7.3 Hz, 2H, 2 × L1–HAr ), 6.85 (d, J = 7.0 Hz, 2H, 2 × L10 –HAr ), 6.46
(s, 1H, L10 –HNH ), 4.66 (t, J = 6.9 Hz, 1H, L10 –HCH= ), 3.03-2.91 (m, 2H, L1–HCH2 ), 2.90–2.81 (m, 2H,
L1–HCH2 ), 2.77 (t, J = 6.3 Hz, 2H, L10 –HCH2 ), 2.37 (s, 3H, L10 –HCH3 ), 2.34 (t, J = 6.1 Hz, 2H, L1–HCH2 ),
2.26 (s, 2H, L1–HCH2 ), 2.21 (s, 3H, L1–HCH3 ), 2.01 (d, J = 6.2 Hz, 6H, 2 × L1–HPhCH3 ), 1.95–1.88 (m,
2H, 2 × L1–HCH2 ), 1.82 (s, 4H, L1–HCH2 ), 1.72 (t, J = 5.7 Hz, 4H, L1–HCH2 ), 1.60 (d, J = 5.3 Hz, 4H,
L1–HCH2 ), 1.54 (s, 4H, L1–HCH2 ). 13 C-NMR (CDCl3 , 100 MHz, TMS): δ 173.7, 167.5, 156.6, 155.0, 148.1,
137.4, 135.9, 134.4, 134.0, 128.1, 127.9, 125.5, 125.3 125.1, 124.1, 124.0,123.9, 123.5, 123.3, 121.6, 40.6, 40.5,
34.2, 34.1, 33.9, 33.7, 32.4, 31.9, 27.2, 26.3, 26.0, 25.9, 25.8, 24.1, 22.9, 18.5, 17.0, 16.9. FTIR (KBr, cm−1 ):
3372 (νN–H , w), 2946 (s), 2864 (m), 1642(νC=N , m), 1564 (w), 1455 (s), 1359 (m), 1302 (w), 1261 (m), 1192
(m), 1164 (w), 1118 (w), 1088 (m), 1032 (w), 848 (w), 805 (w), 746 (s). Anal. Calcd for C36 H43 N3 : C,
83.51, H, 8.37, N, 8.12; Found: C, 83.18, H, 8.61, N, 8.43%.
Molecules 2019, 24, 1176 13 of 20

Ar = 2-(C6 H11 )-6-MeC6 H3 (L2/L20 ). Using a similar procedure and molar ratios to that described for
L1/L10 but with 2-cyclohexyl-6-methylphenylamine hydrochloride as the amine, L2/L20 was obtained as
a yellow oil (0.22 g, 39.7%) with molar ratio of L2/L20 = 1/0.11 (detected by 1 H-NMR).1 H-NMR (CDCl3 ,
400 MHz, TMS): δ 8.38 (t, J = 8.5 Hz, 1H, L2–HPy ), 8.24 (d, J = 7.8 Hz, 1H, L20 –HPy ), 7.68 (d, J = 7.7 Hz,
1H, L20 –HPy ), 7.63 (d, J = 7.6 Hz, 1H, L2–HPy ), H), 7.14 (t, J = 8.1 Hz, 2H, 2 × L2–HAr and 2 × L20 –HAr ),
7.05 (m, 2H, 2 × L2–HAr and 2 × L20 –HAr ), 6.99 (d, J = 7.3 Hz, 2H, 2 × L2–HAr ), 6.94 (s, 2H, 2 × L20 –HAr ),
6.41 (s, 1H, L20 –HNH– ), 4.66 (t, J = 6.9 Hz, 1H, L20 –HCH= ), 2.96 (t, J = 6.0 Hz, 2H, L2–HCH2 ), 2.79–2.71 (m,
2H, L2–HCH2 ), 2.64 (s, 2H, L20 –HCH2 ), 2.38 (s, 3H, L20 –HCH3 ), 2.34 (t, J = 6.3 Hz, 2H, L2–HCH2 ), 2.28 (s,
2H, L2–HCH2 ), 2.21 (s, 3H, L2–HCH3 ), 2.01 (d, J = 5.0 Hz, 6H, 2 × L2–HCH3-Ph ), 1.97 (s, 2H, 2 × L2–HCH2 ),
1.91–1.82 (m, 4H, L2–HCH2 ), 1.78–1.67 (m, 8H, 2 × L2–HCH2 ), 1.53 (s, 8H, 2 × L2–HCH2 ). 13 C-NMR (CDCl3 ,
100 MHz, TMS): δ 173.9, 167.5, 156.7, 155.1, 148.1, 137.5, 146.4, 138.2, 137.5, 135.9, 135.8, 135.4, 128.1, 128.0,
124.4, 124.0, 123.5, 123.4, 39.2, 38.8, 34.1, 33.6, 33.5, 33.2, 32.4, 31.2, 27.5, 27.3, 26.6, 26.3, 24.1, 18.6, 17.1. FT-IR
(KBr, cm−1 ): 3379 (νN–H , w), 2951 (s), 2866 (m), 1644 (νC=N , m), 1564 (w), 1457 (s), 1362 (m), 1303 (w), 1268
(m), 1195 (m), 1164 (w), 1121 (w), 1088 (m), 1033 (w), 850 (w), 805 (w), 747 (s). Anal. Calcd for C38 H47 N3 : C,
83.62, H, 8.68, N, 7.70; Found: C, 83.89, H, 8.31, N, 8.07.
Ar = 2-(C8 H15 )-6-MeC6 H3 (L3/L30 ). Using a similar procedure and molar ratios to that described for
L1/L10 , but with 2-cyclooctyl-6-methylphenylamine hydrochloride as the amine, L3/L30 was obtained
as a yellow powder (0.21 g, 34.5%) with molar ratio of L3/L30 = 1/0.28 (detected by 1 H-NMR). 1 H-NMR
(CDCl3 , 400 MHz, TMS): δ 8.38 (m, 1H, L3–HPy ), 8.24 (d, J = 7.6 Hz, 1H, L30 –HPy ), 7.68 (d, J = 7.3 Hz, 1H,
L30 –HPy ), 7.63 (d, J = 8.0 Hz, 1H, L3–HPy ), 7.12 (t, J = 5.1 Hz, 2H, 2 × L3–HAr and 2 × L30 –HAr ), 7.05–6.96
(m, 2H, 2 × L3–HAr and 2 × L30 –HAr ), 6.92 (d, J = 7.4 Hz, 2H, 2 × L3–HAr and 2 × L30 –HAr ), 6.35 (s, 1H,
L30 –HNH ), 4.64 (t, J = 6.5 Hz, 1H, L30 –HCH= ), 2.99–2.93 (m, 2H, L3–HCH2 ), 2.78–2.74 (m, 2H, L3–HCH2 ), 2.38
(s, 3H, L30 –HCH3 ), 2.34 (t, J = 7.4 Hz, 2H, L3–HCH2 ), 2.29 (s, 2H, L3–HCH2 ), 2.22 (s, 3H, L3–HCH3 ), 2.01 (d,
J = 6.2 Hz, 6H, 2 × L3–HCH3-Ph ), 1.88 (s, 2H, 2 × L3–HCH2 ), 1.88–1.76 (m, 8H, 2 × L3–HCH2 ), 1.72–1.59 (m,
8H, 4 × L3–HCH2 ), 1.53 (s, 8H, 2 × L3–HCH2 ). 13 C-NMR (CDCl3 , 100 MHz, TMS): δ 173.7, 167.5, 156.6,
155.0, 148.1,147.5, 146.4, 138.2, 137.5, 135.9, 134.4, 134.0, 127.9, 127.8,127.7, 125.3, 125.1, 124.9, 124.6, 123.7,
123.4, 121.7, 118.5, 38.4, 35.5, 34.4, 33.9, 33.3, 32.7, 31.9, 27.2, 26.9, 26.8, 26.6, 26.5, 26.2, 24.0, 18.8, 18.7, 18.4,
17.4. FT-IR (KBr, cm−1 ): 3377 (νN–H , w), 2952 (s), 2865 (m), 1644 (νC=N , m), 1567 (w), 1456 (s), 1363 (m),
1304 (w), 1267 (m), 1198 (m), 1164 (w), 1123 (w), 1090 (m), 1033 (w), 851 (w), 806 (w), 749 (s). Anal. Calcd for
C42 H55 N3 : C, 83.81, H, 9.21, N, 6.98; Found: C, 84.12, H, 9.06, N, 6.68%.
Ar = 2-(C5 H9 )-6-Me2 C6 H2 (L4/L40 ). Using a similar procedure and molar ratios to that described for
L1/L10 but with 2-cyclopentyl-4,6-dimethylphenylamine hydrochloride as the amine, L4/L40 was
obtained as a yellow powder (0.20 g, 36.6%) with molar ratio of L4/L40 = 1/0.09 (detected by 1 H-NMR).
1 H-NMR (CDCl , 400 MHz, TMS): δ 8.39 (t, J = 6.9 Hz, 1H, L4–H ), 8.26 (d, J = 8.2 Hz, 1H, L40 –H ),
3 Py Py
7.69 (d, J = 7.6 Hz, 1H, L40 –HPy ), 7.61 (d, J = 8.3 Hz, 1H, L4–HPy ), 7.18 (t, J = 8.5 Hz, 2H, 2 × L4–HAr ),
7.13 (t, J = 5.6 Hz, 2H, 2 × L40 –HAr ), 7.07 (t, J = 6.8 Hz, 2H, 2 × L4–HAr and 2 × L40 –HAr ), 6.97 (d,
J = 7.2 Hz, 2H, 2 × L4–HAr ), 6.82 (d, J = 6.7 Hz, 2H, 2 × L40 –HAr ), 6.46 (s, 1H, L40 –HNH ), 4.66 (t,
J = 7.2 Hz, 1H, L40 –HCH= ), 3.01–2.94 (m, 2H, L4–HCH2 ), 2.89–2.78 (m, 2H, L4–HCH2 ), 2.77 (t, J = 6.3 Hz,
2H, L40 –HCH2 ),2.37 (s, 3H, L40 –HCH2 ), 2.34 (t, J = 6.1 Hz, 2H, L4–HCH2 ), 2.26 (s, 2H, L4–HCH2 ), 2.21 (s,
3H, L4–HCH3 ), 2.01 (d, J = 6.2 Hz, 6H, 2 × L4–HCH3-Ph ), 1.96 (s, 6H, 2 × L4–HCH3-Ph ), 1.88–1.83 (m,
2H, 2 × L4–HCH2 ), 1.81 (s, 4H, L4–HCH2 ), 1.74 (t, J = 5.7 Hz, 4H, L4–HCH2 ), 1.61 (d, J = 5.3 Hz, 4H,
L4–HCH2 ), 1.54 (s, 4H, L4–HCH2 ). 13 C-NMR (CDCl3 , 100 MHz, TMS): δ 173.4, 167.3, 156.6, 155.1, 147.9,
137.6, 136.2, 134.5, 134.2, 128.1, 127.9, 125.3, 125.3 125.3, 123.8, 124.1, 123.9, 123.7, 123.3, 121.8, 40.6, 40.2,
34.3, 34.1, 33.8, 33.7, 32.4, 31.6, 27.3, 26.3, 26.0, 25.9, 25.8, 24.0, 23.1, 18.5, 17.4, 16.9. FT-IR (KBr, cm−1 ):
3376 (νN–H , w), 2949 (s), 2869 (m), 1646 (νC=N , m), 1565 (w), 1458 (s), 1363 (m), 1307 (w), 1264 (m), 1195
(m), 1164 (w), 1119 (w), 1091 (m), 1033 (w), 849 (w), 804 (w), 747 (s). Anal. Calcd for C38 H47 N3 : C,
83.62, H, 8.68, N, 7.70; Found: C, 83.37, H, 8.92, N, 7.59%.
Ar = 2-(C6 H11 )-6-Me2 C6 H2 (L5/L50 ). Using a similar procedure and molar ratios to that described
for L1/L10 but with 2-cyclohexyl-4,6-dimethylphenylamine hydrochloride as the amine, L5/L50 was
Molecules 2019, 24, 1176 14 of 20

obtained as a yellow powder (0.22 g, 38.5%) with molar ratio of L5/L50 = 1/0.12 (detected by 1 H-NMR).
1 H-NMR (CDCl3 , 400 MHz, TMS): δ 8.37 (t, J = 8.4 Hz, 1H, L5–HPy ), 8.24 (d, J = 8.0 Hz, 1H, L50 –HPy ),
7.66 (d, J = 7.6 Hz, 1H, L50 –HPy ), 7.62 (d, J = 7.6 Hz, 1H, L5–HPy ), 7.14 (t, J = 8.1 Hz, 2H, 2 × L5–HAr
and 2 × L50 –HAr ), 7.02 (m, 2H, 2 × L5–HAr and 2 × L50 –HAr ), 6.96 (d, J = 7.1 Hz, 2H, 2 × L5–HAr ),
6.93 (s, 2H, 2 × L50 –HAr ), 6.40 (s, 1H, L50 –HNH ), 4.65 (t, J = 6.9 Hz, 1H, L50 –HCH= ), 2.94 (t, J = 6.7 Hz,
2H, L5–HCH2 ), 2.83–2.76 (m, 2H, L5–HCH2 ), 2.67 (s, 2H, L50 –HCH2 ), 2.42 (s, 3H, L50 –HCH3 ), 2.38 (t,
J = 6.4 Hz, 2H, L5–HCH2 ), 2.31 (s, 2H, L5–HCH2 ), 2.26 (s, 3H, L5–HCH2 ), 2.05 (d, J = 5.0 Hz, 6H, 2 ×
L5–HCH3-Ph ), 2.01 (s, 6H, 2 × L5–HCH3-Ph ), 1.97 (s, 2H, 2 × L5–HCH2 ), 1.88–1.82 (m, 4H, L5–HCH2 ),
1.77–1.65 (m, 8H, 2 × L5–HCH2 ), 1.54 (s, 8H, 2 × L5–HCH2 ). 13 C-NMR (CDCl3 , 100 MHz, TMS): δ 174.1,
167.8, 156.9, 155.4, 148.2, 137.7, 146.4, 138.3, 137.5, 135.9, 135.7, 135.4, 128.2, 128.0, 124.4, 124.1, 123.5,
123.3, 39.4, 39.0, 34.3, 33.7, 33.4, 33.1, 32.4, 31.2, 27.6, 27.4, 26.5, 26.3, 24.0, 18.6, 17.2. FT-IR (KBr, cm−1 ):
3379 (νN–H , w), 2951 (s), 2864 (m), 1645 (νC=N , m), 1563 (w), 1457 (s), 1364 (m), 1301 (w), 1272 (m), 1194
(m), 1164 (w), 1120 (w), 1089 (m), 1034 (w), 850 (w), 804 (w), 748 (s). Anal. Calcd for C40 H51 N3 : C,
83.72, H, 8.96, N, 7.32; Found: C, 83.45, H, 8.73, N, 7.58%.
Ar = 2-(C8 H15 )-6-Me2 C6 H2 (L6/L60 ). Using a similar procedure and molar ratios to that described
for L1/L10 but with 2-cyclooctyl-4,6-dimethylphenylamine hydrochloride as the amine, L6/L60 was
obtained as a yellow powder (0.20 g, 32.1%) with crude molar ratio of L6/L60 = 1/0.21 (detected by
1 H-NMR). 1 H-NMR (CDCl , 400 MHz, TMS): δ 8.41 (m, 1H, L6–H ), 8.27 (d, J = 7.6 Hz, 1H, L60 –H ),
3 Py Py
7.70 (d, J = 7.3 Hz, 1H, L60 –HPy ), 7.66 (d, J = 8.0 Hz, 1H, L6–HPy ), 7.15 (t, J = 6.1 Hz, 2H, 2 × L6–HAr and
2 × L60 –HAr ), 7.11–6.99 (m, 2H, 2 × L6–HAr and 2 × L60 –HAr ), 6.94 (d, J = 7.7 Hz, 2H, 2 × L6–HAr and
2 × L60 –HAr ), 6.38 (s, 1H, L60 –HNH ), 4.66 (t, J = 6.9 Hz, 1H, L60 –HCH= ), 3.07–3.01 (m, 2H, L6–HCH2 ),
2.81–2.75 (m, 2H, L6–HCH2 ), 2.42 (s, 3H, L60 –HCH3 ), 2.35 (t, J = 7.4 Hz, 2H, L6–HCH2 ), 2.33 (s, 2H,
L6–HCH2 ), 2.25 (s, 3H, L6–HCH3 ), 2.11 (d, J = 6.0 Hz, 6H, 2 × L6–HCH3-Ph ), 2.03 (d, J = 5.9 Hz, 6H, 2
× L6–HCH3-Ph ), 1.90 (s, 2H, 2 × L6–HCH2 ), 1.88–1.76 (m, 8H, 2 × L6–HCH2 ), 1.71–1.60 (m, 8H, 4 ×
L6–HCH2 ), 1.51 (s, 8H, 2 × L6–HCH2 ). 13 C-NMR (CDCl3 , 100 MHz, TMS): δ 174.6, 168.1, 157.3, 155.5,
148.5,147.9, 146.6, 138.3, 137.8, 136.2, 134.4, 134.1, 128.3, 127.9, 127.7, 125.7, 125.4, 124.9, 124.8, 123.7,
123.6, 121.9, 118.5, 38.4, 36.0, 34.6, 33.9, 33.4, 32.5, 32.0, 27.4, 26.9, 26.7, 26.4, 26.3, 26.0, 24.1, 18.8, 18.6,
18.2, 17.4. FT-IR (KBr, cm−1 ): 3374 (νN–H , w), 2948 (s), 2865 (m), 1644 (νC=N , m), 1565 (w), 1459 (s), 1361
(m), 1303 (w), 1263 (m), 1194 (m), 1165 (w), 1119 (w), 1090 (m), 1036 (w), 851 (w), 805 (w), 749 (s). Anal.
Calcd for C44 H59 N3 : C, 83.89, H, 9.44, N, 6.67; Found: C, 83.63, H, 9.26, N, 6.98%.

3.3. Synthesis of [2-(1-ArN) C2 H3 -9-ArN-5,6,7,8-C5 H8 C5 H3 N] CoCl2 (Co1–Co6)

Ar = 2-(C5 H9 )-6-MeC6 H3 (Co1). The ligand L1/L10 (110.0 mg, 0.23 mmol) and CoCl2 ·6H2 O (47.3 mg,
0.20 mmol) were dissolved in 5 mL of ethanol. The reaction mixture was stirred at room temperature for
overnight after which time diethyl ether (30 mL) was added to precipitate the complex. The precipitate
was collected by filtration and washed with diethyl ether (3 × 5 mL), followed by drying under
vacuum to give complex Co1 as a light brown powder (122.0 mg, 94.0%). FT-IR (KBr, cm−1 ): 2947 (s),
2863 (m), 2167 (w), 2138 (w), 2012 (w), 1992 (w), 1608 (νC=N , m), 1571 (s), 1454 (s), 1369 (m), 1309 (w),
1257 (s), 1198 (s), 1113 (m), 1086 (w), 934 (w), 888 (w), 845 (m), 744 (vs). Anal. Calcd for C36 H43 Cl2 CoN3 :
C, 66.77, H, 6.69, N, 6.49; Found: C, 66.42, H, 6.61, N, 6.55%.
Ar = 2-(C6 H11 )-6-MeC6 H3 (Co2). Using a similar procedure and molar ratios to that described for Co1
but with L2/L20 as the ligand, the complex Co2 was obtained as the light brown powder in 126.0 mg
(yield: 93.5%). FT-IR (KBr, cm−1 ): 2923 (s), 2851 (m), 2168 (w), 2119 (w), 2022 (w), 1989 (w), 1606 (νC=N ,
m), 1570 (s), 1448 (s), 1369 (m), 1314 (w), 1260 (m), 1230 (s), 1194 (s), 1114 (m), 1088 (w), 936 (w), 886
(w), 846 (m), 774 (vs), 736 (w). Anal. Calcd for C38 H47 Cl2 CoN3 : C, 67.55, H, 7.01, N, 6.22; Found: C,
67.77, H, 6.94, N, 6.34%..
Ar = 2-(C8 H15 )-6-MeC6 H3 (Co3). Using a similar procedure and molar ratios to that described for Co1
but with L3/L30 as the ligand, the complex Co3 was obtained as the light brown powder in 130.0 mg
Molecules 2019, 24, 1176 15 of 20

(yield: 91.2%). FT-IR (KBr, cm−1 ): 2916 (s), 2853 (m), 2167 (w), 2082 (w), 2014 (w), 1989 (w), 1609 (νC=N ,
m), 1569 (s), 1465 (s), 1368 (m), 1313 (w), 1257 (s), 1193 (s), 1114 (m), 1085 (w), 931 (w), 845 (m), 771 (vs),
735 (w). Anal. Calcd for C42 H55 Cl2 CoN3 : C, 68.94, H, 7.58, N, 5.74; Found: C, 69.31, H, 7.47, N, 5.89%.
Ar = 2-(C5 H9 )-4,6-Me2 C6 H2 (Co4). Using a similar procedure and molar ratios to that described for Co1
but with L4/L40 as the ligand, the complex Co4 was obtained as the light brown powder in 126.0 mg
(yield: 93.3%). FT-IR (KBr, cm−1 ): 2916 (s), 2857 (m), 2166 (w), 2078 (w), 2032 (w), 1991 (w), 1609 (νC=N , m),
1569 (s), 1472 (s), 1448 (s), 1368 (m), 1311 (w), 1257 (s), 1205 (s), 1113 (m), 1085 (w), 926 (w), 850 (s), 768 (s).
Anal. Calcd for C38 H47 Cl2 CoN3 : C, 67.55, H, 7.01, N, 6.22; Found: C, 67.82, H, 7.31, N, 6.06%.
Ar = 2-(C6 H11 )-4,6-Me2 C6 H2 (Co5). Using a similar procedure and molar ratios to that described
for Co1 but with L5/L50 as the ligand, the complex Co5 was obtained as the light brown powder in
135.0 mg (yield: 95.6%). FT-IR (KBr, cm−1 ): 2918 (vs), 2852 (s), 2169 (w), 2111 (w), 2011 (w), 1989 (w),
1611 (νC=N , m), 1569 (s), 1447 (s), 1367 (m), 1313 (w), 1258 (s), 1204 (m), 1116 (w), 1086 (w), 850 (s), 768
(s). Anal. Calcd for C40 H51 Cl2 CoN3 : C, 68.27, H, 7.31, N, 5.97; Found: C, 67.89, H, 7.47, N, 6.33%.
Ar = 2-(C8 H15 )-4,6-Me2 C6 H2 (Co6). Using a similar procedure and molar ratios to that described
for Co1 but with L6/L60 as the ligand, the complex Co6 was obtained as the light brown powder in
133.0 mg (yield: 87.4%). FT-IR (KBr, cm−1 ): 2916 (s), 2854 (m), 2166 (w), 2112 (w), 2012 (w), 1990 (w),
1611 (νC=N , m), 1568 (s), 1466 (s), 1441 (s), 1368 (m), 1314 (w), 1257 (m), 1212 (m), 1114 (w), 1084 (w),
926 (w), 852 (s), 768 (s). Anal. Calcd for C44 H59 Cl2 CoN3 : C, 69.55, H, 7.83, N, 5.53; Found: C, 69.81, H,
7.58, N, 5.85%.

3.4. X-ray Crystallographic Studies

Single-crystal X-ray diffraction studies of Co1 and Co3 were conducted on a Rigaku Sealed Tube
CCD (Saturn 724+) diffractometer with graphite-mono chromated Mo-Kα radiation (λ = 0.71073 Å) at
173(2) K and the cell parameters obtained by global refinement of the positions of all collected reflections.
Intensities were corrected for Lorentz and polarization effects and empirical absorption. The structures
were solved by direct methods and refined by full-matrix least-squares on F2 . All non-hydrogen atoms
were refined anisotropically and all hydrogen atoms were placed in calculated positions. Structure solution
and refinement were performed by using the SHELXT (Sheldrick, 2015) [55]. The disorder displayed by
the carbon atoms in Co3 was processed by the SHELXL-2015 software [56]. Crystal data and processing
parameters for Co2 and Co3 are summarized in Table 4. X-ray crystallographic data in CIF for the
Cambridge Crystallographic Data Centre (CCDC) 1,897,124 (Co2) and 1,897,125 (Co3) are available free of
charge from The Cambridge Crystallographic Data Centre.

Table 4. Crystal data and structure refinement for Co2 and Co3.

Co2 Co3
CCDC No. 1897124 1897125
Crystal color Brown Yellow
Empirical formula C38 H47 Cl2CoN3 C42 H55 Cl2CoN3
Formula weight 675.61 731.72
Temperature (K) 173.15 173.15(2)
Wavelength (Å) 0.71073 0.71073
Crystal system orthorhombic tetragonal
Space group Fdd2 I41 /a
a (Å) 33.4157(6) 34.3337(8)
b (Å) 31.4531(6) 34.3337(8)
c (Å) 16.9829(4) 14.5297(7)
α (◦ ) 90 90
β (◦ ) 90 90
γ (◦ ) 90 90
Volume (Å3 ) 17849.5(6) 17127.7(11)
Z 16 16
Dcalcd (g cm−3 ) 1.006 1.135
µ (mm−1 ) 0.528 0.555
F(000) 5712.0 6224.0
Molecules 2019, 24, 1176 16 of 20

Table 4. Cont.

Co2 Co3
Crystal size (mm3 ) 0.288 × 0.193 × 0.102 0.274 × 0.144 × 0.118
θ rang (◦ ) 4.56–63.054 3.044–66.158
Limiting indices −46 ≤ h ≤ 48, −43 ≤ k ≤ 46, −24 ≤ l ≤ 23 −50 ≤ h ≤ 48, −47 ≤ k ≤ 51, −21 ≤ l ≤ 10
No. of rflns collected 70088 49080
No. unique rflns [R(int)] 0.0625(10266) 0.1028(4627)
Completeness to θ (%) 93.0 (θ = 25.00) 90.6 (θ = 25.00)
Goodness of fit on F2 1.040 0.971
Final R indices [I > 2σ(I)] R1 = 0.0625, wR2 = 0.1560 R1 = 0.1028, wR2 = 0.2154
R indices (all data) R1 = 0.0868, wR2 = 0.1705 R1 = 0.2894, wR2 = 0.3034
Largest diff. peak and hole (e Å−3 ) 0.41 and −0.21 0.42 and −0.42

3.5. General Procedure for Ethylene Polymerization under 5/10 Atm Pressure
A 250 mL stainless steel autoclave (Dalian Sanling Electronic Manufacture, Dalian, China),
equipped with an ethylene pressure control system, a mechanical stirrer and a temperature controller,
was employed for the reaction. The autoclave was evacuated and refilled with ethylene three times.
When the desired reaction temperature was reached, toluene, the co-catalyst (MAO or MMAO),
and a toluene solution of the catalytic precursor (the total volume was 100 mL) were injected into the
autoclave by using syringes. Then, the ethylene pressure was increased to 5/10 atm, maintained at
this level with constant feeding of ethylene. After the reaction was carried out for their quired period,
the reactor was cooled with a water bath and the excess ethylene was vented. The reaction solution
was quenched with 10% HCl/ethanol. The precipitated polymer was collected through filtration,
washed with ethanol and dried under vacuum at 60 ◦ C until constant weight.

4. Conclusions
A family of six cobalt (II) chloride complexes, Co1–Co6, bound by single ring-fused
2-(1-cycloalkylphenylimino)ethyl-9-cycloalkylphenylimino-5,6,7,8-tetrahydrocyclo-heptapyridines,
was prepared by the reaction of the corresponding carbocyclic-fused NNN-pincer ligands
(L1/L10 –L6/L60 ) and cobalt(II) chloride and fully characterized. On activation with either MMAO
or MAO, all these ortho cycloalkyl substituted cobalt complexes displayed good activity for
ethylene polymerization with the optimum temperature of 50 ◦ C, affording the linear polyethylene.
The molecular weight (Mw = 9.78–25.6 kg mol−1 ) is higher than that observed with their analogues
D bearing alkyl substituent. The ring size of the ortho substituent greatly affected their molecular
weight and polymerization activity, which was demonstrated by the highest activity achieved by
the cyclopentyl substituted ones (Co1 and Co4) and the highest molecular weight by cyclooctyl
substituted ones (Co3 and Co6). Notably, polyethylene using MAO as activator displayed high
selectivity for vinyl end-groups (–CH=CH2 ), while with MMAO the polyethylene possessed both the
saturated and saturated linear structure.

Author Contributions: Design of the study and experiments, W.Z. and W.-H.S.; synthesis and catalysis, J.G., Z.W.,
I.I.O., I.V.O. and A.V.; manuscript, W.Z. and W.-H.S.; interpretation of the data obtained from the single crystal
X-ray diffraction, Y.S.; chemical support, X.H.
Funding: This work was supported by the National Natural Science Foundation of China (Nos. 51473170,
21871275 and 51861145303) and the Russian Foundation for Basic Research (No. 18-53-80031_BRICS/5171102116).
A.V thanks the Chinese Academy of Sciences President’s International Fellowship Initiative for the award of
post-doctoral fellowship (Grant No. 2018PM0012).
Conflicts of Interest: The authors declare no conflict of interest.
Molecules 2019, 24, 1176 17 of 20

Abbreviations
PE Polyethylene
ORTEP Oak Ridge Thermal Ellipsoid Plot
CIF Calibration Index File
GPC Gel Permeation Chromatography
MAO methylaluminoxane
MMAO Modified methylaluminoxane
PDI Polydispersity index
Tm Melting temperature

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Sample Availability: Samples of the organic compounds and cobalt complexes are available from the authors.

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