Discovery and evaluation of highly active imidotitanium ethylene polymerisation catalysts using high throughput catalyst screening

Adams, Nico; Arts, Henricus J.; Bolton, Paul D.; Cowell, Dan; Dubberley, Stuart R.; Friederichs, Nic; Grant, Craig M.; Kranenburg, Mirko; Sealey, Andrew J.; Wang, Bing; Wilson, Paul; Cowley, Andrew R.; Mountford, Philip; Schröder, Martin

doi:10.1039/b313921b

Cited by 68 publications

(86 citation statements)

References 20 publications

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“…Adams et al reported on the discovery of new imidotitanium catalysts for the polymerization of ethylene. [309] The catalysts were prepared by semi-automated parallel syntheses from 50 commercially available amines. While details on the polymers and catalysts are given, no details on the highthroughput polymerization screening methods used are provided.…”

Section: Polymerization Catalysts For Polyolefinsmentioning

confidence: 99%

Combinatorial and High‐Throughput Materials Science

2007

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There is increasing acceptance of high-throughput technologies for the discovery, development, and optimization of materials and catalysts in industry. Over the years, the relative synchronous development of technologies for parallel synthesis and characterization has been accompanied by developments in associated software and information technologies. This Review aims to provide a comprehensive overview on the state of the art of the field by selected examples. Technologies developed to aid research on complex materials are covered as well as databases, design of experiment, data-mining technologies, modeling approaches, and evolutionary strategies for development. Different methods for parallel synthesis provide single sample libraries, gradient libraries for electronic or optical materials, similar to polymers and catalysts, and products produced through formulation strategies. Many examples illustrate the variety of isolated solutions and document the barely recognized variety of new methods for the synthesis and analysis of almost any material. The Review ends with a summary of success stories and statements on still-present problems and future tasks.

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Section: Polymerization Catalysts For Polyolefinsmentioning

confidence: 99%

Combinatorial and High‐Throughput Materials Science

2007

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“…[1][2][3][4][5][6][7] Both computational and experimental studies have been performed to probe the structure and reactivity of these systems. It has been shown that Group 4 transition-metal imides have potential in CÀH activation chemistry, [8][9][10][11][12][13][14][15][16] materials chemistry [17][18][19][20] and olefin polymerisation catalysis (with the imide acting as an "ancillary ligand"), [21][22][23] and that these systems can be utilised in an wide variety of stoichiometric and sometimes catalytic coupling reactions with unsaturated substrates. [6] Terminal titanium imido complexes were first structurally characterised in 1990, [24,25] and since then a large number of imido complexes with different ancillary ligands have been synthesised.…”

Section: Introductionmentioning

confidence: 99%

Titanium Imido Complexes of Cyclooctatetraenyl Ligands

Dunn

Hazari

Jones

et al. 2005

Chemistry A European J

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Reaction of [Ti(NR)Cl2(py)3] (R=tBu or 2,6-iPr2C6H3) with K(2)[COT] (COT=C8H8) or Li2[COT''] (COT''=1,4-C8H6(SiMe3)2) gave the monomeric complexes [Ti(NR)(eta8-COT)] or [Ti(NR)(eta8-COT'')], respectively. The pseudo-two coordinate, "pogo stick" geometry for these complexes is unique in both early transition-metal and cyclooctatetraenyl ligand chemistry. In contrast, reaction of [Ti(N-2,6-Me2C6H3)Cl2(py)3] with K2[COT] gave the mu-imido-bridged dimer [Ti2(mu-N-2,6-Me2C6H3)2(eta8-COT)2]. It appears that as the steric bulk of the imido and C8 ring substituents are decreased, dimerisation becomes more favourable. Aryl imido COT complexes were also prepared by imido ligand exchange reactions between anilines and [Ti(NtBu)(eta(8)-COT)] or [Ti(NtBu)(eta(8)-COT'')]. The complexes [Ti(NtBu)(eta(8)-COT)], [Ti(N-2,6-iPr2C6H3)2(eta8-COT)] and [Ti2(mu-N-2,6-Me2C6H3)2(eta8-COT)2] have been crystallographically characterised. The electronic structures of both the monomeric and dimeric complexes have been investigated by using density functional theory (DFT) calculations and gas-phase photoelectron spectroscopy. The most striking aspect of the bonding is that binding to the imido nitrogen atom is primarily through sigma and pi interactions, whereas that to the COT or COT'' ring is almost exclusively through delta symmetry orbitals. A DFT-based comparison between the bonding in [Ti(NtBu)(eta8-COT)] and the bonding in the previously reported late transition-metal "pogo stick"complexes [Os(NtBu)(eta6-C6Me6)], [Ir(NtBu)(eta5-C5Me5)] and [Ni(NO)(eta5-C5H5)] has also been undertaken.

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“…[50][51][52] In particular, high-throughput methods have recently been used to discover a range of olefin polymerisation catalysts. [53][54][55][56][57] While these methods have been used in the evaluation of lanthanide catalysts, 58 their use has not flourished in contrast to their utility in organotransition metal chemistry. This may be due to the perception that lanthanide based catalysts are less robust and more reactive than their transition metal counterparts.…”

Section: Introductionmentioning

confidence: 99%