Molecular Catalysis 553 (2024) 113782

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Molecular Catalysis
journal homepage: www.journals.elsevier.com/molecular-catalysis

Research Paper

Bis(imino)pyridine vanadium (III) and cobalt (II) complexes catalyzed

selective dimerization of propylene
Zhi Luo a, 1, *, Jialei Gao b, 1, Mengshuai Li c, Zhi Wen a, Huayi Li a, *
a
Beijing National Laboratory of Molecular Sciences, CAS Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190,
China
b
College of Chemistry and Environmental Science, Hebei University, Baoding, Hebei 071002, China
c
College of Chemistry, Zhengzhou University, Zhengzhou, Henan 450001, China

A R T I C L E I N F O A B S T R A C T

Keywords: The high-value utilization of propylene is a topic worthy of in-depth research. In this regard, a series of bis
Propylene dimerization (imino)pyridine vanadium (III) and cobalt (II) complexes have been synthesized and employed to selectively
Selectivity produce valuable products, such as 4-methyl-1-pentene (4M1P) and 1-hexene (1-H), through propylene dimer­
bis(imino)pyridine Vanadium (III) and Cobalt
ization with methylaluminoxane (MAO) as a cocatalyst. The study found that when halogen substituents are
(II)
Catalytic mechanism
introduced on the pyridine group, the catalyst’s activity improves significantly. A clear reaction mechanism has
been proposed: to produce 4M1P, a two-step 2,1-insertion process is involved, with catalysts having lower steric
hindrance proving more favorable for achieving high selectivity. On the other hand, the production of 1-H in­
volves a one-step 1,2-insertion followed by a one-step 2,1-insertion process. Although the steric hindrance effect
benefits the initial 1,2-insertion step, it hampers the subsequent 2,1-insertion step. The steric hindrance effect
counteracts the impact of the central metal, leading to a decrease in selectivity.

1. Introduction upon this knowledge, bis(imino)pyridine vanadium (III) complexes

Propylene occupies a significant position in the petrochemical in­
dustry, primarily due to its status as an olefin primarily utilized in the
production of polypropylene [1–4]. Moreover, the oligomerization
offspring of propylene are employed as gasoline additives and as pre­
cursors for an array of other chemicals [5–11]. Among them, 4-Meth­
yl-1-pentene (4M1P) [12–13], a dimerization product, is leveraged in
the generation of polymers (co)polymers exhibiting outstanding optical,
thermal, and electrical features [14]. Additionally, 1-hexene (1-H) [15],
another dimerization product, another dimerization product, serves as a
co-monomer for the copolymerization with ethylene, resulting in the
formation of linear low-density polyethylene (LLDPE). All these appli­
cations correspond to products with an increased overall value relative
to the initial olefin.
Because of these developments, there is growing interest in propyl­
ene selective dimerization using homogeneous catalysts [16–20]. The
discovery of highly active iron olefin polymerization catalysts in the late
1990s sparked significant interest in the chemistry of transition metal
complexes with tridentate bis(imino)pyridine ligands [21]. Building
were synthesized and initially employed by the Alt group [22] for se­
lective synthesis of 4M1P and bis(imino)pyridine cobalt (II) complexes
[23] were synthesized and employed by Small [24] to selective synthesis
of 1-H (Scheme 1). Their research revealed that the substitutions of the
imino groups have significant impacts on the composition and distri­
bution of dimers. Despite that the propylene dimerization catalyst is
industrially important and some works on mechanism research have
been reported [25–26], the mechanism of propylene dimerization still
needs further exploration.
In this study, we report the successful application of bis(imino)pyr­
idine vanadium (III) and cobalt (II) complexes, in combination with
methylaluminoxane (MAO) as a cocatalyst, for the selective dimeriza­
tion of propylene. The main focus of our investigation was to determine
the impact of substitutions on the pyridine group on the activity and
selectivity of the catalyst. Additionally, we conducted a comprehensive
analysis of the dimers and control experiments to gain a deeper under­
standing of the reaction mechanism involved in propylene dimerization.

* Corresponding authors.
E-mail addresses: luozhi@iccas.ac.cn (Z. Luo), lihuayi@iccas.ac.cn (H. Li).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.mcat.2023.113782
Received 20 October 2023; Received in revised form 12 December 2023; Accepted 13 December 2023
Available online 17 December 2023
2468-8231/© 2023 Elsevier B.V. All rights reserved.
Z. Luo et al.
2. Experimental
2.1. Materials
Toluene was distilled from Na under nitrogen. Methyl aluminoxane
(MAO, 30 wt.% in toluene), VCl3(THF)3 and CoCl2 were purchased from
J&K Scientific. All other chemical reagents and solvents were obtained
from commercial sources and used without purification.
2.2. Characterization
1
H NMR spectra and 13C NMR spectra of ligands were carried out on
a Bruker 400 MHz at room temperature in CDCl3. The products of the
oligomerization experiments were characterized by a gas chromato­
graph (PE Clarus 580) and GCMS– (FOCUS DSQTM Thermo Scientific).
Mass spectra were recorded on a Varian MAT CH7 instrument (direct
inlet system, electron impact ionization 70 eV). Elemental analyses were
performed with a VarioEl III CHN instrument.
2.3. Synthesis of the bis(imino)pyridine vanadium (III) and cobalt (II)
complexes
The bis(imino)pyridine vanadium (III) and cobalt (II) complexes
were prepared according to the previously reported procedure with
some modifications[27]. In a typical example, the vanadium (III) and
cobalt (II) complexes were carried out as follows (Scheme 2).
General procedure for the synthesis of bis(imino)pyridine (1
and 3): MAO/SiO2 pellets (3.0 g) were added to a solution of diac­
etylpyridine (3.5 mmol) in toluene. After the addition of 4-methyl-3-flu­
oro-aniline (1.31 g, 10.5 mmol) or 2-isopropylaniline (1.42 g, 10.5
mmol), the solution was heated at 50 ◦ C for 24 h. The reaction was
monitored by TLC. After the raw material was completely consumed, the
solvent was removed by vacuum distillation, and the residue was poured
Scheme. 1. Selective dimerization of propylene catalyzed by bis(imino)pyridine vanadium (III) and cobalt (II) complexes.
2
Molecular Catalysis 553 (2024) 113782
into methanol. The yellow solid product was separated out, dried and
collected.
2,6-Bis(1-(3-methyl-4-fluorophenimine)ethyl)pyridine (1a): 0.90 g,
68 % yield, yellow powder. 1H NMR (400 MHz, CDCl3) δ 8.32 (d, J =
7.8 Hz, 2H), 7.86 (t, J = 7.8 Hz, 1H), 7.17 (t, J = 8.3 Hz, 2H), 6.54 (dd, J
= 8.2, 4.4 Hz, 4H), 2.41 (s, 6H), 2.28 (s, 6H). 13C NMR (101 MHz,
CDCl3) δ 167.95, 162.75, 160.31, 155.33, 150.59, 150.50, 136.88,
131.66, 131.60, 122.46, 119.67, 119.50, 114.82, 114.79, 106.62,
106.38, 16.23, 14.11, 14.08. 19F NMR (377 MHz, CDCl3) δ − 116.63.
HRMS (ESI) Calculated for C23H20F2N3 [M-H]− 376.1625, found
376.1632.
4-Chloro-2,6-bis(1-(3-methyl-4-fluorophenimine)ethyl)pyridine
(1b): 1.42 g, 68 % yield, yellow powder. 1H NMR (400 MHz, CDCl3): δ
8.33 (s, 2H), 7.18 (t, J = 8.2 Hz, 2H), 6.54 (dd, J = 8.2, 4.3 Hz, 4H), 2.40
(s, 6H), 2.28 (s, 6H). 13C NMR (101 MHz, CDCl3): δ 166.94, 162.73,
160.29, 156.65, 150.02, 145.43, 131.80, 122.57, 119.95, 114.70, 16.39,
14.08. 19F NMR (377 MHz, CDCl3) δ − 116.42. HRMS (ESI) Calculated
for C23H21ClF2N3 [M + H]+ 412.1388, found 412.1392.
4-Bromo-2,6-bis(1-(3-methyl-4-fluorophenimine)ethyl)pyridine
(1c): 1.53 g, 67 % yield, yellow powder. 1H NMR (400 MHz, CDCl3) δ
8.50 (s, 2H), 7.18 (t, J = 8.2 Hz, 2H), 6.70–6.38 (m, 4H), 2.39 (s, 6H),
2.28 (s, 6H). 13C NMR (101 MHz, CDCl3) δ 166.83, 162.73, 160.29,
156.37, 150.07, 149.98, 131.72, 131.66, 125.63, 120.03, 119.86,
114.75, 114.72, 16.25, 14.12, 14.08. 19F NMR (377 MHz, CDCl3) δ
− 116.41. HRMS (ESI) Calculated for C23H21BrF2N3 [M + H]+ 456.0887,
found 456.0887.
4-Trifluoromethyl-2,6-bis(1-(3-methyl-4-fluorophenimine)ethyl)
pyridine (1d): 1.28 g, 58 % yield, yellow powder. 1H NMR (400 MHz,
CDCl3) δ 8.58 (s, 2H), 7.19 (t, J = 8.2 Hz, 2H), 6.62–6.50 (m, 4H), 2.44
(s, 6H), 2.29 (s, 6H). 13C NMR (101 MHz, CDCl3) δ 166.79, 162.74,
160.30, 156.69, 149.94, 139.74, 139.40, 131.77, 120.11, 114.65,
106.44, 16.35, 14.10. 19F NMR (377 MHz, CDCl3) δ − 64.43, − 116.34.
HRMS (ESI) Calculated for C24H21F5N3 [M + H]+ 446.1652, found
Z. Luo et al.
Scheme. 2. Synthesis of the vanadium (III) and cobalt (II) complexes.
446.1656.
4-Methylcarboxy-2,6-bis(1-(3-methyl-4-fluorophenimine)ethyl)pyr­
idine (1e): 1.31 g, 61 % yield, yellow powder. 1H NMR (400 MHz,
CDCl3) δ 8.85 (s, 2H), 7.18 (t, J = 8.3 Hz, 2H), 6.62–6.47 (m, 4H), 3.98
(s, 3H), 2.43 (s, 6H), 2.28 (s, 6H). 13C NMR (101 MHz, CDCl3) δ 167.20,
162.73, 160.29, 156.50, 150.20, 138.82, 131.60, 121.84, 119.85,
114.73, 52.90, 16.38, 14.16. 19F NMR (377 MHz, CDCl3) δ − 116.50.
HRMS (ESI) Calculated for C25H24F2N3O2 [M + H]+ 436.1833, found
436.1837.
4-Cyano-2,6-bis(1-(3-methyl-4-fluorophenimine)ethyl)pyridine (1f):
1.30 g, 64 % yield, yellow powder. 1H NMR (400 MHz, CDCl3) δ 8.57 (s,
2H), 7.20 (t, J = 8.2 Hz, 2H), 6.59–6.50 (m, 4H), 2.42 (s, 6H), 2.29 (s,
6H). 13C NMR (101 MHz, CDCl3) δ 166.25, 162.72, 160.28, 156.57,
149.66, 149.57, 131.86, 123.96, 121.60, 120.42, 120.25, 116.41, 16.19,
16.05, 14.11. 19F NMR (377 MHz, CDCl3) δ − 116.21. HRMS (ESI)
Calculated for C24H21F2N4 [M + H]+ 403.1731, found 403.1734.
2,6-Bis(1-(2-isopropylaniline) ethyl)pyridine (3a): 1.12 g, 81 %
yield, yellow powder. 1H NMR (400 MHz, CDCl3) δ 8.41 (d, J = 7.8 Hz,
2H), 7.90 (t, J = 7.6 Hz, 1H), 7.33 (d, J = 7.5 Hz, 2H), 7.16 (dt, J = 29.6,
7.3 Hz, 4H), 6.65 (d, J = 7.5 Hz, 2H), 3.09–2.92 (m, 2H), 2.39 (s, 6H),
1.20 (d, J = 6.7 Hz, 12H). 13C NMR (101 MHz, CDCl3) δ 166.58,
155.51, 148.71, 138.16, 136.81, 126.14, 125.73, 124.05, 122.25,
118.39, 28.48, 22.86, 16.43. HRMS (ESI) Calculated for C27H32N3 [M +
H]+ 398.2596, found 398.2588.
4-Chloro-2,6-Bis(1-(2-isopropylaniline) ethyl)pyridine (3b): 1.08 g,
72 % yield, yellow powder. 1H NMR (400 MHz, CDCl3) δ 8.40 (s, 2H),
7.34 (d, J = 7.6 Hz, 2H), 7.17 (dt, J = 25.1, 7.4 Hz, 4H), 6.62 (d, J = 7.6
Hz, 2H), 3.00 (dt, J = 13.7, 6.9 Hz, 2H), 2.37 (s, 6H), 1.20 (d, J = 6.9 Hz,
12H). 13C NMR (101 MHz, CDCl3) δ 165.62, 156.86, 148.27, 145.33,
138.23, 126.17, 125.79, 124.35, 122.40, 118.29, 118.17, 28.51, 22.97,
22.87, 16.58, 16.46. HRMS (ESI) Calculated for C27H31ClN3 [M + H]+
432.2207, found 432.2201.
4-Bromo-2,6-Bis(1-(2-isopropylaniline) ethyl)pyridine (3c): 1.30 g,
78 % yield, yellow powder. 1H NMR (400 MHz, CDCl3) δ 8.57 (s, 2H),
7.34 (dd, J = 7.6, 1.4 Hz, 2H), 7.16 (dtd, J = 24.7, 7.4, 1.4 Hz, 4H), 6.62
(dd, J = 7.6, 1.4 Hz, 2H), 3.00 (dt, J = 13.8, 6.9 Hz, 2H), 2.36 (s, 6H),
1.20 (d, J = 6.9 Hz, 12H). 13C NMR (101 MHz, CDCl3) δ 165.56,
156.58, 148.29, 138.23, 134.02, 126.19, 125.79, 125.39, 124.36,
118.23, 28.47, 22.95, 16.52. HRMS (ESI) Calculated for C27H31BrN3 [M
+ H]+ 476.1701, found 476.1700.
4-Trifluoromethyl-2,6-Bis(1-(2-isopropylaniline) ethyl)pyridine
(3d): 1.15 g, 71 % yield, yellow powder. 1H NMR (400 MHz, CDCl3) δ
8.64 (s, 2H), 7.35 (d, J = 7.5 Hz, 2H), 7.18 (dt, J = 24.4, 7.3 Hz, 4H),
6.64 (d, J = 7.6 Hz, 2H), 3.00 (dt, J = 13.7, 6.9 Hz, 2H), 2.41 (s, 6H),
1.20 (d, J = 6.9 Hz, 12H). 13C NMR (101 MHz, CDCl3) δ 165.52,
156.87, 148.19, 138.25, 126.21, 125.81, 124.37, 118.23, 28.55, 28.47,
3
Molecular Catalysis 553 (2024) 113782
22.95, 22.84, 16.55, 16.42. 19F NMR (377 MHz, CDCl3) δ − 64.39.
HRMS (ESI) Calculated for C28H31F3N3 M + H]+ 466.2470, found
466.2465.
4-Methylcarboxy-2,6-Bis(1-(2-isopropylaniline) ethyl)pyridine (3e):
1.28 g, 80 % yield, yellow powder. 1H NMR (400 MHz, CDCl3) δ 8.93 (s,
2H), 7.35 (d, J = 7.6 Hz, 2H), 7.17 (dt, J = 26.4, 7.4 Hz, 4H), 6.64 (d, J
= 7.6 Hz, 2H), 4.00 (s, 3H), 3.03 (dt, J = 13.6, 6.8 Hz, 2H), 2.41 (s, 6H),
1.20 (d, J = 6.9 Hz, 12H). 13C NMR (101 MHz, CDCl3) δ 165.93,
165.72, 156.64, 148.49, 138.79, 138.21, 126.16, 125.78, 124.21,
121.57, 118.30, 118.17, 28.48, 28.41, 22.99, 22.87, 16.64, 16.52.
HRMS (ESI) Calculated for C29H34N3O2 M + H]+ 457.2685, found
457.2680.
4-Cyano-2,6-Bis(1-(2-isopropylaniline) ethyl)pyridine (3f): 1.03 g,
70 % yield, yellow powder. 1H NMR (400 MHz, CDCl3) δ 8.64 (s, 2H),
7.36 (d, J = 7.5 Hz, 2H), 7.18 (dt, J = 21.6, 7.4 Hz, 4H), 6.63 (d, J = 7.6
Hz, 2H), 3.00 (dt, J = 13.8, 6.9 Hz, 2H), 2.40 (s, 6H), 1.21 (d, J = 6.9 Hz,
12H). 13C NMR (101 MHz, CDCl3) δ 164.98, 156.77, 147.92, 138.38,
126.21, 125.89, 124.69, 124.64, 123.80, 123.72, 121.53, 118.19,
118.06, 116.75, 28.61, 28.53, 22.97, 22.86, 16.36, 16.24. HRMS (ESI)
Calculated for C28H31N4 M + H]+ 423.2549, found 423.2544.
General procedure for the synthesis of bis(imino)pyridine vanadium
(III) complexes (2) and bis(imino)pyridine cobalt (II) complexes (4): The
bis(imino)pyridine (1.0 mmol) was added in a flask and degassed.
Approximately 15 mL of ether was injected as solvent and added (0.8
mmol) VCl3(THF)3 or CoCl2. The solution was stirred at room temper­
ature overnight. After the reaction stopped, the reaction system was
filtered and the solid was washed with ether. A powder was obtained
after the product had been dried in vacuo.
2a: 0.25 g, 65 % yield, black powder. MALDI-TOF-MS: C23H20F2N3V,
M + H]+: 533.0, found 533.0. 2b: 0.28 g, 62 % yield, black powder.
MALDI-TOF-MS: C23H20Cl3F2N3V, [M-Cl]+: 532.0, found 532.0. 2c:
0.37 g, 75 % yield, black powder. MALDI-TOF-MS: C23H20BrCl2F2N3V,
[M-Cl]+: 578.2, found 578.2. 2d: 0.29 g, 60 % yield, black powder.
MALDI-TOF-MS: C24H20Cl2F5N3V, [M-Cl]+: 566.0, found 566.0. 2e:
0.27 g, 56 % yield, black powder. MALDI-TOF-MS: C25H23Cl2F2N3O2V
[M-Cl]+: 556.1 found 556.1. 2f: 0.26 g, 58 % yield, black powder.
MALDI-TOF-MS: C24H20Cl2F2N4V, [M-Cl]+: 523.0, found 523.0.
4a: 0.32 g, 76 % yield, yellow powder. MALDI-TOF-MS:
C27H31ClCoN3 [M-Cl]+: 491.2, found 491.2. 4b: 0.33 g, 73 % yield,
green powder. MALDI-TOF-MS: C27H30Cl2CoN3 [M-Cl]+: 525.1, found
525.1. 4c: 0.28 g, 58 % yield, green powder. MALDI-TOF-MS:
C27H30BrClCoN3 [M-Cl]+: 569.1, found 569.1. 4d: 0.32 g, 76 % yield,
brown powder. MALDI-TOF-MS: C28H30ClCoF3N3 [M-Cl]+: 559.1, found
559.1. 4e: 0.38 g, 81 % yield, grey powder. MALDI-TOF-MS:
C29H33ClCoN3O2 [M-Cl]+: 549.2, found 549.2. 4f: 0.28 g, 64 % yield,
black powder. MALDI-TOF-MS: C28H30ClCoN4 [M-Cl]+: 516.1, found
Z. Luo et al. Molecular Catalysis 553 (2024) 113782

516.1.
2.4. Dimerization of propylene
The dimerization of propylene was carried out in a 500 mL high-
pressure reactor. The reactor was heated under vacuum and equili­
brated the pressure with nitrogen. 100 (or 40) μmol catalyst in 10 (or 5)
mL solvent was injected into the reactor, and the specified amount of
cocatalyst was added together. With the 50 g of propylene liquid added,
the polymerization begins. After the reaction time was set, the products
were collected, weighed and analyze by GC or GC–MS.
3. Results and discussion
3.1. Bis(imino)pyridine vanadium (III) complexes catalyzed propylene
dimerization to prepare 4M1P
Initial experiments were conducted to explore the propylene selec­
tive dimerization catalyzed by bis(imino)pyridine vanadium (III) com­
plexes, as summarized in Table 1. Under the standard conditions, it was
observed that the catalyst 2a exhibited a promising activity of 1.8 × 104
g olig. mol− 1 V complex h− 1 and a good 4M1P selectivity of 59 % (entry
1). The oligomers were mainly dimers (84 %), with a small amount of
trimer (14 %) and tetramer (2 %). Decreased (entry 2) or increased
(entry 3) the equivalence of MAO could reduce the selectivity of 4M1P,
but increased the equivalence of MAO could help improve the activity
(3.2 × 104 g olig. mol− 1 V complex h− 1) and dimerization selectivity (86
%) of the catalyst 2a. With the polymerization temperature decreased,
the composition of oligomers had little effect, but it would reduce the
catalyst activity (entry 4). On the contrary, increased the polymerization
temperature would increase the catalyst activity, but it was not condu­
cive to the selectivity of the catalyst (entry 5).
The 4-substituted bis(imino)pyridine vanadium (III) complexes were
also used as catalysts for propylene selective dimerization (entry 6–10).
It was observed that the activity could be significantly improved by
introducing halogen substituents (-Cl and -Br) on the pyridine group (2b
and 2c), while maintaining good selectivity (56 % and 53 %, respec­
tively). Among the catalysts tested, the one with a -CF3 substituent (2d)
exhibited the highest activity, reaching 7.2 × 104 g olig. mol− 1 V com­
plex h− 1, but its selectivity was only 28 % (entry 8). The catalyst with a
-COOMe substituent (2e) showed not significant effect on activity and
selectivity (entry 14). Interestingly, the catalyst with a -CN substitution
(2f) achieved the best selectivity with 61 % for 4M1P, although the
activity was not good (entry 15). It has been observed that the sub­
stituents on the pyridine group were located distantly from the catalytic
center. Therefore, the activity and selectivity of the catalyst primarily
rely on electronic effects. The introduction of suitable electron-
withdrawing groups (-Cl, -Br, and -CF3) reduced the electron cloud
density around the active center. This adjustment promotes elimination
reactions, leading to enhanced catalyst activity and influencing the
composition of the resulting products.
3.2. Bis(imino)pyridine cobalt (II) complexes catalyzed propylene
dimerization to prepare 1-H
Unlike bis(imino)pyridine vanadium (III) complexes that catalyzed
propylene oligomerization to obtain branched olefins, bis(imino)pyri­
dine cobalt (II) complexes were more likely to obtain straight chain
olefins. All the bis(imino)pyridine cobalt (II) complexes 4a-4f were used
to catalyzed propylene dimerization to prepare 1-H, as summarized in
Table 2. Under the standard conditions, it was observed that the catalyst
4a exhibited a good activity of 0.7 × 105 g olig. mol− 1 Co complex h− 1
and a good 1-H selectivity of 60 % (entry 11). Dimers (92 %) and trimers
(8 %) were the main products, with only a very small amount of tetra­
mers (0.1 %). It was also observed that the activity could be significantly
improved by introducing halogen substituents (-Cl and -Br) on pyridine
group (entry 12, 4b and entry 13, 4c), while maintaining good selec­
tivity (54 %). However, with the other electron-withdrawing substituent
groups (-CF3, -COOMe, and -CN) onto pyridine, the activity of the cat­
alysts (4d, 4e and 4f) significantly decreased (entry 14 and 15) or even
became inactive (entry 16). According to the above experimental re­
sults, the catalyst not only did it not improve the activity, but may also

Table. 1
Bis(imino)pyridine vanadium (III) complexes catalyzed selective dimerization of propylene.

entrya cat. Productivity TON 4M1P% C6% C9% C12%

(g olig. mol− 1 V complex h− 1)

1 2a 1.8 × 104 506 59 84 14 2

2b 2a 1.1 × 104 293 56 83 15 2
3c 2a 3.2 × 104 869 57 86 13 1
4d 2a 0.9 × 104 253 59 84 15 1
5e 2a 2.8 × 104 680 51 82 16 2
6 2b 4.9 × 104 1307 56 83 15 2
7 2c 5.0 × 104 1261 53 83 15 2
8 2d 7.2 × 104 960 28 80 18 2
9 2e 2.9 × 104 773 56 83 15 2
10 2f 0.4 × 104 116 61 81 19 0
a
Standard conditions: 100 μmol 2; 6.7 mL MAO (4.5 M in toluene); 50 g propylene; 25 ◦ C; 4 h. TON: moles of 4M1P per mole of pre-catalyst. 4M1P %: g(4M1P)/g
(oligomers). C6 %: g(C6)/g(oligomers). C9 %: g(C9)/g(oligomers). C12 %: g(C12)/g(oligomers).
b
MAO: 100 eq.
c
MAO: 500 eq.
d
Reaction temperature: 0 ◦ C.
e
Reaction temperature: 50 ◦ C.

4
Z. Luo et al. Molecular Catalysis 553 (2024) 113782

Table. 2
Bis(imino)pyridine cobalt (II) complexes catalyzed selective dimerization of propylene.

entrya cat. Productivity TON 1-H% C6% C9% C12%

(g olig. mol− 1 Co complex h − 1
)

11 4a 0.7 × 105 1250 60 92 8 0 (0.1)

12 4b 1.1 × 105 1767 54 83 16 0 (0.3)
13 4c 1.4 × 105 2250 54 85 15 1 (0.7)
14 4d 0.4 × 105 607 51 87 12 0 (0.4)
15 4e 0.3 × 105 491 55 93 7 0 (0.3)
16 4f (trace) – – – –
17b 4c 0.8 × 105 1286 54 87 12 1 (0.8)
18c 4c 1.9 × 105 2884 51 82 18 0 (0.3)
19d 4c 0.7 × 105 1167 56 88 11 0 (0.4)
20e 4c 1.6 × 105 1952 41 75 24 1 (0.6)
a
Standard conditions: 40 μmol 4; 0.9 mL MAO (4.5 M in toluene); 50 g propylene; 25 ◦ C; 2.5 h. TON: moles of 1-H per mole of pre-catalyst. 1-H %: g(1-H)/g
(oligomers). C6 %: g(C6)/g(oligomers). C9 %: g(C9)/g(oligomers). C12 %: g(C12)/g(oligomers).
b
MAO: 50 eq.
c
MAO: 200 eq.
d
Reaction temperature: 0 oC.
e
Reaction temperature: 50 oC.

lead to catalyst deactivation, when its substituents have strong electron-
withdrawing ability.
The influence of polymerization conditions on catalyst activity and
product selectivity had also been emphasized. When the equivalent of
MAO was reduced, the activity of the catalyst 4c decreased, the selec­
tivity of 1-H remained, and the dimerization selectivity improved (entry
17). Similar to bis(imino)pyridine vanadium (III) complexes, when bis
(imino)pyridine cobalt (II) complexes catalyze propylene oligomeriza­
tion, increased MAO equivalent (entry 18) or reaction temperature
(entry 20) was beneficial for improving reaction activity, but it was not
conducive to the selectivity of the target product. It should be noted that
lowered the reaction temperature also reduced the activity, but the
selectivity of 1-H could effectively improve catalyzed by 4c (entry 19).
3.3. General process of propylene dimerization catalyzed by transition
metal
In homogeneous catalysis, the mechanism of alkene oligomerization
has been extensively investigated [28]. Some theoretical studies [26] on
olefin oligomerization [29] based on transition metal have been inves­
tigated, including the most classic Cossee-Arlman mechanism [30–32].
Based on this mechanism, the dimerization of propylene can lead to 8
dimers via coordination, double insertion and elimination reactions [25,
33]. The general process and products [34] are shown in Scheme 3.
3.4. Products and possible process of propylene dimerization catalyzed by
bis(imino)pyridine vanadium (III) and cobalt (II) complexes

GC and GC–MS techniques were employed to analyze the

Scheme. 3. General process and products of propylene dimerization.

5
Z. Luo et al.
composition and content of oligomers, as well as to determine the
residence time of each dimer using the external standard method. For
accurate quantification, n-pentadecane was used as the internal
standard.
In order to obtain a clearer mechanism, as shown in Fig. 1, dimers
were carefully distinguished. The products of bis(imino)pyridine vana­
dium (III) complexes catalyzed propylene dimerization include 4M1P,
2,3-dimethyl-1-butene (DM1B), (E)-4-methyl-2-pentene (E-4M2P), (Z)-
4-methyl-2-pentene (Z-4M2P) and 2-methyl-1-pentene (2M1P). The
products of propylene dimerization catalyzed by bis(imino)pyridine
cobalt (II) complexes were relatively simple, only 1-H, (E)-2-pentene (E-
1-H), and (Z)-2-pentene (Z-1-H).
According to the generation path of dimers, possible mechanisms
[35–36] have been proposed (Fig. 2). Firstly, bis(imino)pyridine vana­
dium (III) or cobalt (II) complexes reacted with MAO to obtain a "V-H" or
"Co-H" species with catalytic activity. Then the "V-H" or "Co-H" species
coordinated with the propylene molecule. For the catalysts designed in
this article, the "V-H" species were more inclined to undergo 2,1-inser­
tion to obtain the "V-isopropyl" species, while the "Co-H" species
choose to undergo 1,2-insertion to obtain the "Co-n-propyl" species.
Next, the "V-isopropyl" species or "Co-n-propyl" species coordinated with
the next propylene molecule. The second insertion reaction was mainly
carried out in the form of 2,1-insertion for both "V-isopropyl" and
"Co-n-propyl" species. Finally, the dimers were obtained by β-H elimi­
nation while releasing the catalyst to complete the catalytic cycle [23].
Due to the small steric hindrance of the vanadium (III) complexes
involved in this article, the insertion of vanadium species was more
inclined towards a 2,1-insertion approach. Similarly, due to the lack of
steric hindrance effects, some vanadium species also underwent 1,2-
insertion to obtain corresponding dimers, such as 2M1P and DM1B.
On the contrary, due to the large steric hindrance of the cobalt (II)
complexes mentioned in this article, the first insertion of cobalt species
tended to be done in a 1,2-insertion manner. However, from the
composition of the dimer, it could be seen that the second insertion was
Fig. 1. GC trace of propylene oligomers catalyzed by bis(imino)pyridine vanadium (III) complexes (up) and bis(imino)pyridine cobalt (II) complexes (down).
6
Molecular Catalysis 553 (2024) 113782
carried out using a 2,1-insertion manner. It was believed that the
manner of the second insertion was determined by the central metal
cobalt, although this was not conducive to the steric hindrance effect.
The selectivity of α-olefins or internal olefins was primarily influenced
by the catalyst structure, with the reaction temperature also played a
significant role. This observation helps explain why reducing the poly­
merization temperature enhances the selectivity of 1-hexene (1-H), as
demonstrated in entry 19 compared to entry 13.
3.5. Some control experiments
Based on the above analysis, it is believed that the steric hindrance of
the catalyst plays a crucial role in the composition of the product. To
further demonstrate the proposed mechanism, some control experi­
ments were designed.
As expected, the bulk bis(imino)pyridine vanadium (III) complexes 5
catalyzed propylene dimerization to obtain mainly 2M1P, which was
obtained through two 1,2-insertion paths (Scheme 4). Similarly, when
the bis(imino)pyridine cobalt (II) complexes 6 with greater steric hin­
drance catalyzed propylene oligomerization, the selectivity of 1-H
sharply decreased. Although the steric hindrance effect was advanta­
geous for the 1,2-insertion in the first step, it was disadvantageous for
the 2,1- insertion in the second step. The steric hindrance effect coun­
teracted the effect of the central metal, resulting in a decreased in
selectivity.
In addition, it was found that the target product also underwent some
side reactions under the action of the catalyst (Scheme 5). Under the
standard conditions, both 4M1P and 1-H underwent isomerization and
dimerization to obtain corresponding by-products. Therefore, to obtain
highly selective target products, in addition to optimizing the catalyst
structure, controlling the conversion rate is also a factor that needs to be
considered.
Z. Luo et al. Molecular Catalysis 553 (2024) 113782

Fig. 2. Possible mechanism of propylene dimerization catalyzed by bis(imino)pyridine vanadium (III) complexes (left) and bis(imino)pyridine cobalt (II) com­
plexes (right).

Scheme. 4. Propylene dimerization catalyzed by bulk bis(imino)pyridine vanadium (III) complexes 5 and bis(imino)pyridine cobalt (II) complexes 6.

Scheme. 5. Side reactions of propylene dimerization.

4. Conclusions
A series of bis(imino)pyridine vanadium (III) and cobalt (II) com­
plexes have been synthesized and used as catalysts to promote propylene
dimerization in the presence of methylaluminoxane as a cocatalyst. The
vanadium (III) complexes demonstrate high selectivity for producing
4M1P during propylene dimerization, while the cobalt (II) complexes
yield 1-hexene as the dominant product. Surprisingly, the substituents
on the pyridine group of these catalysts had minimal impact on selec­
tivity but significantly influenced their activity. In particular, the
introduction of halogen substituents noticeably boosted the catalyst’s
activity. We have also proposed a relatively clear dimerization mecha­
nism. The formation of 4M1P follows a two-step 2,1-insertion process,
whereas 1-hexene is produced through a sequential 1,2-insertion fol­
lowed by a 2,1-insertion pathway. The steric hindrance of the catalysts
played a significant role in determining the insertion pathway. The
substantial steric hindrance favored the selectivity of 1,2-insertion.
Additionally, the choice of central metal also impacted the insertion
path. When aiming for highly selective target products, optimizing the
catalyst structure and controlling the conversion rate are both essential
considerations.
CRediT authorship contribution statement
Zhi Luo: Funding acquisition, Investigation, Supervision, Writing –
original draft, Writing – review & editing. Jialei Gao: Data curation,
Investigation, Visualization, Writing – original draft. Mengshuai Li:
Data curation, Formal analysis. Zhi Wen: Data curation, Formal anal­
ysis. Huayi Li: Methodology, Supervision, Validation, Visualization,
Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial

7
Z. Luo et al.
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgement
Financially supported by the National Natural Science Foundation of
China (22201287). The authors also acknowledge Prof. Youliang Hu
(ICCAS) and Dr. Ying Ying (Institute of grassland research of CAAS) for
helpful discussion.
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.mcat.2023.113782.
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