Synthesis of Ti (IV) complexes of donor-functionalised

phenoxy-imine tridentates and their evaluation in

ethylene oligomerisation and polymerisation
James A. Suttil,a Miranda F. Shaw,a David S. McGuinness, Michael G.
Gardinera and Stephen J. Evans

Nguyen Xuan Dieu Linh

Erasmus Sucat 2022-2024

1
 Contents

Introduction Synthesis of
1 Introduction of Phenoxy-imine
ligands
2 Catalysts
Synthesis of Ligands and
Complexes

Conclusion
3 Polymerization results 4 The selectivity of Ethylene
conversion
Polymerization of Ethylene

2
Introduction

3
 Overview on Phenoxy-imine ligands

❖ Phenoxy-imine ligands have been employed as ligands in ethylene

polymerization systems for a wide range of metals
❖ In 2009, researchers from Mitsui Chemicals first disclosed in the patent
literature a highly active trimerization system based on phenoxy-imine
motif
❖ 4 mono-anionic tridentate phenoxy-imine ligands were prepared and
reacted with Ti4+ to give catalysts (Mono-ligand) complexes
❖ Catalysts were tested for their potential as ethylene oligomerization/
polymerization systems in conjunction with MethylAlumiOxane activator

4
Synthesis of Catalysts

5
 Synthesis of ligands
Suzuki cross-cpouling

PdCl2, PPh3
  K2CO3

2-Bromo-aniline 2-(methylthio)- 2-(2’-(methylthio)-

phenylboronic acid phenyl) aniline

Suzuki cross-cpouling

PdCl2, PPh3
  K2CO3

2- Bromo-N- 2-methoxyphenyl- 2-(2′-methoxyphenyl)-N-

methylaniline boronic acid methylaniline
6
 Synthesis of ligands
Imine formation

  Et2O

3-tert-Butyl- 2-methyl-3-methoxy-
salicylaldehyde propyl-2-amine Ligand 1

Imine formation

CH2Cl2
 

2-(2’-(methylthio)- 2-hydroxy-5-methyl-3-(1-
phenyl) aniline adamantyl )-benzaldehyde Ligand 2
7
 Synthesis of ligands
Silicone-protected alcohol

n-butyllithium
  (CH3)3SiCl
THF, -78oC

Trimethylsilyl
Ligand 1 chloride Ligand 3

Synthesis of higher amine

THF, NEt3
 

2-(2′-methoxyphenyl)-N- 3,5-Di-tert-butyl-2-
methylaniline hydroxybenzyl bromide Ligand 4
8
 Synthesis of catalysts

DCM, -95oC
  TiCl4(thf)2

Ligand 3 Complex 5

Toluene, -95oC
  TiCl4

Ligand 4 Complex 6
9
 Synthesis of catalysts

Toluene, -95oC
  TiCl4

Ligand 2 Complex 7

10
Ethylene polymerization

11
 Reaction conditions and set up

Cat./
MethylAluminOxane
(MAO)

Conditions: 20 µmol catalyst loading, toluene (50 ml), 5 bar ethylene, 30oC,
30 min

Reactor: 0.3 L stainless steel Parr 5500 Compact Mini Reactor

Polymer formed: remove by filtration, wash and dry at 60oC for 3 days

Samples of reaction mixture: analyzed by GC-MS

12
 Ethylene polymerization

The applied catalysts

Complex IV Complex 5 Complex 6 Complex 7

13
Results & Discussion

14
 Polymerization results
Entry Catalyst MAO eq. Activityb %1-Butene %1-Hexene %1-C8 %Polyethylene

1 IV 300 236 0.5 87.5 9.0 3.0

2 5 300 0.6 7.4 0.7 - 91.9

3 6 300 14 1.1 1.6 1.0 96.3

4 7 300 24 0.5 11.3 1.3 86.9

Complex 5 showed the lowest activity and an interesting selectivity towards 1-butene
Complex 6 yielded a series of even-numbered linear alpha olefins from C 4–C28

Among 3 synthesized compounds (5,6,7), complex 7 gave the greatest selectivity towards
1-hexene
: kg product {(mol metal) h bar -1}-1
b

15
Entry Catalyst MAO eq. Activityb %1-Butene %1-Hexene %1-C8 %Polyethylene

4 7 300 24 0.5 11.3 1.3 86.9

5 7 400 29 0.3 9.7 0.3 89.7

6 7 1000 28 0.3 3.5 0.3 95.9

7 7 200 7 Trace 24.8 - 75.2

8 7 100 13 0.9 0.3 1.3 97.5

Increase of MAO concentration suggested a reduction in the concentration

of the ethylene trimerization catalyst (lower 1-hexene product)
MAO = 100 => Insufficient activator is present to generate the targeted
catalytic species
: kg product {(mol metal) h bar-1}-1
b

16
 Discussion

- For complex 5: short alkyl-chains (less than four

carbons) between the imine functionality and the
donor moiety can lead to a selectivity shift from
ethylene oligomerization to polymerization
- A hard Lewis basic donor considerably limited the
Motif of the form [−ONO] can
activity of catalyst readily stabilize the Ti(IV)
metal center in conjunction
with MAO

- For complex IV: the conjugation between the

phenoxide anion and the imine moiety plays an
important role in stabilizing the catalyst towards
ethylene trimerization

17
 Discussion
For complex 7:
- The change of color from pale-yellow to deep puple proved
the reduction of Ti (IV) to Ti (III)
- Compounds of the form [−ONS] were shown to readily
undergo reduction in the presence of MAO activator
- The majority of the 1-hexene is formed in the initial period
when the catalyst reduces to form Ti (III)
- 1-hexene is expected to result from a Ti(II)/Ti(IV) cycle
- Catalyst activated with MAO before contact with ethylene
showed that most catalyst is reduced to the Ti (III) species at
the initial time
18
 Polymerization mechanism

The form of Oligomers resulted from a Metallacycle mechanism, and might

be due to the change of oxidation state of Ti (IV)
The form of Polymer most likely resulted from a Cossee mechanism

React. Chem. Eng., 2022, 7, 133-141 19

 Conclusion
❖ A number of analogues to the Mitsui (Ti phenoxy-imine) ethylene
trimerization system were prepared
❖ The Ti phenoxy-imine catalyst is clearly sensitive to changes in the bridging
group linking the third donor atom, the identity of this donor and changes to
the imine donor
❖ The best result with respect to ethylene trimerization belonged to complex 7
❖ The challenge in obtaining selective oligomerization with these systems
therefore seems to lie in control of multi-mechanism behavior of Ti
complexes/MAO catalyst
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