Tridentate Aryloxy‐Based Titanium Catalysts towards Ethylene Oligomerization and Polymerization

Audouin, Hugo; Bellini, Rosalba; Magna, Lionel; Mézailles, Nicolas; Olivier‐Bourbigou, Hélène

doi:10.1002/ejic.201500721

Cited by 8 publications

(10 citation statements)

References 52 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Previously published ligands HL1 18 and HL2 19 were prepared using well established synthetic protocols. Previously published ligands HL1 18 and HL2 19 were prepared using well established synthetic protocols.…”

Section: Resultsmentioning

confidence: 99%

“…No further purification or drying operations have been performed. 18 Ligand HL1 was prepared following published procedures. Solvents were purified via a Pure-Solv MD-4-EN solvent purification system from Innovative Technology, Inc. Methanol was refluxed over activated magnesium for at least 24 h and then distilled prior to use.…”

Section: Methodsmentioning

confidence: 99%

“…The metal precursors [MoO2(acac)2] 20 and [MoO2Cl2(DME)] 21 were synthesized according to known procedures. 18 (m), 1120 (s), 876 (w). The 1 H, 13 C and 31 P NMR spectra were recorded on a Bruker Optics instrument at 300/75/121 MHz.…”

Section: Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Oxygen activation and catalytic aerobic oxidation by Mo(iv)/(vi) complexes with functionalized iminophenolate ligands

et al. 2016

View full text Add to dashboard Cite

Synthesis of molybdenum(vi) dioxido complexes 1-3, coordinated by one or two functionalized iminophenolate ligands HL1 or HL2, bearing a donor atom side chain or a phenyl substituent, respectively, allowed for systematic investigation of the oxygen atom transfer (OAT) reactivity of such complexes towards phosphanes. Depending on stoichiometry and employed phosphane (PMe3 or PPh3), different molybdenum(iv) and molybdenum(v) complexes 4-7 were obtained. Whereas molybdenum(iv) complexes 4 and 5, bearing a terminal PMe3 ligand, readily reacted with molecular O2 to form oxido peroxido complexes 8 and 9, phosphane free μ-oxido bridged dinuclear molybdenum(v) complexes 6 and 7 proved to be stable towards oxidation with molecular O2 under ambient conditions. Single-crystal X-ray diffraction analyses revealed different isomeric structures in the solid state for dioxido complexes 1 and 2 in comparison with oxido phosphane complex 5, dinuclear oxido μ-oxido complex 6 and oxido peroxido complexes 8 and 9, pointing towards an isomeric rearrangement during OAT. Compounds 1 and 2 were furthermore tested for their ability to catalyze the aerobic oxidation of PMe3 and PPh3. A significant difference in catalytic activity has been observed in the oxidation of PMe3, where complex 1 bearing donor atom functionalized ligands led to higher conversion and selectivity than complex 2 coordinated by phenyl iminophenolate ligands. In the oxidation of PPh3, complex 2 leads to higher conversion compared to 1. In a control experiment, phenyl-based dinuclear μ-oxido complex 7, derived from complex 2, was found to be catalytically active, which suggests a lower energy barrier for disproportionation into [MoO(L)2] and [MoO2(L)2] in comparison with methoxypropylene based compound 6, a prerequisite for subsequent reactivity toward molecular O2.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Oxygen activation and catalytic aerobic oxidation by Mo(iv)/(vi) complexes with functionalized iminophenolate ligands

et al. 2016

View full text Add to dashboard Cite

show abstract

“…of MAO polymerize ethylene with activity not exceeding 7–8 kg mol −1 (Ti) h −1 . [ 26 ] A complex [cis‐TiCl 2 ( 3 ‐2,2′‐oxydiethanol)(THF)] (compound XI , Figure 2) has been synthesized and structurally characterized by X‐ray diffraction (XRD) [ 27 ] ; however, the catalytic activity of this compound has not been investigated. A dichloro oxovanadium(V) alkoxide complex XII with a similar ligand environment, activated with diethyl aluminum chloride as cocatalyst and in the presence of methyl trichloroacetate as promoter, exhibits remarkably higher activity (445 kg mol −1 (V) h −1 bar −1 ) than VOCl 3 (360 kg mol −1 (V) h −1 bar −1 ) towards ethylene polymerization.…”

Section: Introductionmentioning

confidence: 99%

Novel titanium(IV) diolate complexes with additional O‐donor as precatalyst for the synthesis of ultrahigh molecular weight polyethylene with reduced entanglement density: Influence of polymerization conditions and its implications on mechanical properties

Тuskaev

Гагиева

Kurmaev

et al. 2021

Applied Organom Chemis

View full text Add to dashboard Cite

New alkoxo‐titanium(IV) complexes with diolate ligand containing additional donor oxygen atom have been synthesized from readily available and scalable precursors. The structure of complex 4 was established by X‐ray diffraction. Titanium atom adopts a distorted tetrahedral geometry formed by six oxygen atoms of ligands. The resulting complexes 3–4 are moderately or highly active in ethylene polymerization in the presence of {EtnAlCl3–n + Bu2Mg} binary cocatalysts. The influence of the nature of the solvent, the organoaluminum cocatalyst and the polymerization temperature on the activity of catalytic systems, and the properties of the resulting polymers were studied. The obtained polymers are linear polyethylene of ultrahigh molecular weight (up to 5.8·106 g mol−1) with a broad molecular weight distribution. The polymers are suitable for the modern methods of polymer processing—the solventless solid‐state formation of super high‐strength (breaking strength up to 2.8 GPa) and high‐modulus (elastic modulus up to 140 GPa) oriented films and film tapes. The possibility of scaling up the synthesis of ultrahigh molecular weight polyethylene (UHMWPE) without a significant drop in the productivity of the catalytic system and polymer properties is shown. UHMWPE samples have been investigated by small‐angle X‐ray scattering (SAXS) methods to study the structural changes induced by solid‐state drawing of nascent reactor powders.

show abstract

“…Most of the reported literature on titanium-based trimerization systems focused on improving and rationalizing the oligomerization reaction, paying little attention to polymerization. [8][9][10][11][12][13][14][15][16][17][18][19][20] On the one hand, applying the ligandoriented catalyst design strategy, Fujita and coworkers reported the strong dependence between ligand structure and the reactivity of trimerization phenoxy-imine systems. 9 Indeed, 1hexene selectivity and activity can be tuned by subtle changes of substituents on specific positions of the phenyl rings.…”

Section: Introductionmentioning

confidence: 99%

Titanium-based phenoxy-imine catalyst for selective ethylene trimerization: effect of temperature on the activity, selectivity and properties of polymeric side products

Cordier

Breuil

Michel

et al. 2020

Catal. Sci. Technol.

Self Cite

View full text Add to dashboard Cite

show abstract

Tridentate Aryloxy‐Based Titanium Catalysts towards Ethylene Oligomerization and Polymerization

Cited by 8 publications

References 52 publications

Oxygen activation and catalytic aerobic oxidation by Mo(iv)/(vi) complexes with functionalized iminophenolate ligands

Oxygen activation and catalytic aerobic oxidation by Mo(iv)/(vi) complexes with functionalized iminophenolate ligands

Novel titanium(IV) diolate complexes with additional O‐donor as precatalyst for the synthesis of ultrahigh molecular weight polyethylene with reduced entanglement density: Influence of polymerization conditions and its implications on mechanical properties

Titanium-based phenoxy-imine catalyst for selective ethylene trimerization: effect of temperature on the activity, selectivity and properties of polymeric side products

Contact Info

Product

Resources

About