Imperial College London

ProfessorGeorgeBritovsek

Faculty of Natural SciencesDepartment of Chemistry

Professor of Chemistry
 
 
 
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Contact

 

+44 (0)20 7594 5863g.britovsek Website

 
 
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Location

 

501GMolecular Sciences Research HubWhite City Campus

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Summary

 

Publications

Publication Type
Year
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120 results found

Young CT, von Goetze R, Tomov AK, Zaccaria F, Britovsek GJPet al., 2020, The Mathematics of Ethylene Oligomerisation and Polymerisation, TOPICS IN CATALYSIS, ISSN: 1022-5528

Journal article

Tay DWP, Nobbs JD, Romain C, White AJP, Aitipamula S, van Meurs M, Britovsek GJPet al., 2020, gem-dialkyl effect in diphosphine Ligands: synthesis, coordination behavior, and application in Pd-catalyzed hydroformylation, ACS Catalysis, Vol: 10, Pages: 663-671, ISSN: 2155-5435

A series of palladium complexes with C3-bridged bidentate bis(diphenylphosphino)propane ligands with substituents of varying steric bulk at the central carbon have been synthesized. The size of the gem-dialkyl substituents affects the C–C–C bond angles within the ligands and consequently the P–M–P ligand bite angles. A combination of solid-state X-ray diffraction (XRD) and density functional theory (DFT) studies has shown that an increase in substituent size results in a distortion of the 6-membered metal–ligand chair conformation toward a boat conformation, to avoid bond angle strain. The influence of the gem-dialkyl effect on the catalytic performance of the complexes in palladium-catalyzed hydroformylation of 1-octene has been investigated. While hydroformylation activity to nonanal decreases with increasing size of the gem-dialkyl substituents, a change in chemoselectivity toward nonanol via reductive hydroformylation is observed.

Journal article

Vriamont CEJJ, Chen T, Romain C, Corbett P, Manageracharath P, Peet J, Conifer CM, Hallett JP, Britovsek GJPet al., 2019, From lignin to chemicals: Hydrogenation of lignin models and mechanistic insights into hydrodeoxygenation via low-temperature C-O bond cleavage, ACS Catalysis, Vol: 9, Pages: 2345-2354, ISSN: 2155-5435

The catalytic hydrogenation of a series of lignin model compounds, including anisole, guaiacol, 1,2-dimethoxybenzene, 4-propyl-2-methoxyphenol, and syringol, has been investigated in detail, using a Ru/C catalyst in acetic acid as the solvent. Both hydrogenation of the aromatic unit and C–O bond cleavage are observed, resulting in a mixture of cyclohexanes and cyclohexanols, together with cyclohexyl acetates due to esterification with the solvent. The effect on product composition of the reaction parameters temperature (80–140 °C), pressure (10–40 bar), and reaction time (0.5–4 h) has been evaluated in detail. The lignin model compound 4-propyl-2-methoxyphenol was converted to 4-propylcyclohexanol in 4 h at 140 °C and 30 bar of H2 pressure with 84% conversion and 63% selectivity. Mechanistic studies on the reactivity of reaction intermediates have shown that C–O bond cleavage under these relatively mild conditions does not involve a C–O bond hydrogenolysis reaction but is due to elimination and hydrolysis reactions (or acetolysis in acetic acid solvent) of highly reactive cyclohexadiene- and cyclohexene-based enols, enol ethers, and allyl ethers.

Journal article

Malko D, Guo Y, Jones P, Britovsek G, Kucernak Aet al., 2019, Heterogeneous iron containing carbon catalyst (Fe-N/C) for epoxidation with molecular oxygen, Journal of Catalysis, Vol: 370, Pages: 357-363, ISSN: 0021-9517

Pyrolized transition metal and nitrogen containing carbon materials (M-N/C) have shown promising activities as electrocatalysts for oxygen reduction reactions (ORR) in fuel cell cathodes. Similar materials have recently gained interest as heterogeneous catalysts. We report that ORR-active heterogeneous M-N/C materials can catalyze the chemical epoxidation of olefins with molecular oxygen and two equivalents of aldehyde at room temperature and ambient pressure. The observed yield and selectivity is higher than that for homogeneous analogues and the catalysts achieve TOF > 2700 h−1 and TON > 16,000. The ability to recycle the catalyst several times is also demonstrated.

Journal article

Shahruddin S, Jimenez-Serratos G, Britovsek G, Matar O, Muller Eet al., 2019, Fluid-solid phase transition of n-alkane mixtures: Coarse-grained molecular dynamics simulations and diffusion-ordered spectroscopy nuclear magnetic resonance, Scientific Reports, Vol: 9, ISSN: 2045-2322

Wax appearance temperature (WAT), defined as the temperature at which the first solid paraffin crystal appears in a crude oil, is one of the key flow assurance indicators in the oil industry. Although there are several commonly-used experimental techniques to determine WAT, none provides unambiguous molecular-level information to characterize the phase transition between the homogeneous fluid and the underlying solid phase. Molecular Dynamics (MD) simulations employing the statistical associating fluid theory (SAFT) force field are used to interrogate the incipient solidification states of models for long-chain alkanes cooled from a melt to an arrested state. We monitor the phase change of pure long chain n-alkanes: tetracosane (C24H50) and triacontane (C30H62), and an 8-component surrogate n-alkane mixture (C12-C33) built upon the compositional information of a waxy crude. Comparison to Diffusion Ordered Spectroscopy Nuclear Magnetic Resonance (DOSY NMR) results allows the assessment of the limitations of the coarse-grained models proposed. We show that upon approach to freezing, the heavier components restrict their motion first while the lighter ones retain their mobility and help fluidize the mixture. We further demonstrate that upon sub-cooling of long n-alkane fluids and mixtures, a discontinuity arises in the slope of the self-diffusion coefficient with decreasing temperature, which can be employed as a marker for the appearance of an arrested state commensurate with conventional WAT measurements.

Journal article

Fernandez-Alvarez VM, Ho SKY, Britovsek GJP, Maseras Fet al., 2018, A DFT-based mechanistic proposal for the light-driven insertion of dioxygen into Pt(ii)-C bonds, CHEMICAL SCIENCE, Vol: 9, Pages: 5039-5046, ISSN: 2041-6520

Journal article

Nobbs JD, Tomov AK, Young CT, White AJP, Britovsek GJPet al., 2018, From alternating to selective distributions in chromium-catalysed ethylene oligomerisation with asymmetric BIMA ligands, Catalysis Science and Technology, Vol: 8, Pages: 1314-1321, ISSN: 2044-4753

The oligomerisation of ethylene with chromium-based catalysts containing asymmetric BIMA (bis(benzimidazole)methylamine) ligands produces linear alpha olefins (LAOs) that follow an alternating distribution. The catalytic activity and the degree of alternation is affected by the different ligands; in particular variations at the backbone of the ligand affect the nature of the distribution. For certain catalysts a deviation from regular alternating behaviour is observed, whereby increased amounts of 1-hexene and 1-octene (up to 29 mol%) are obtained compared to the amount expected from the distribution analysis based on C₁₀–C₃₄ LAOs. This behaviour towards more selective oligomerisation to 1-hexene and 1-octene can be explained by varying probabilities of single and double ethylene insertion. The deviations will depend on the size of the metallacycle and are most pronounced early on during the metallacycle growth.

Journal article

Britovsek GJP, McGuinness DS, Tomov AK, 2016, Mechanistic study of ethylene tri- and tetramerisation with Cr/PNP catalysts: effects of additional donors, Catalysis Science and Technology, Vol: 6, Pages: 8234-8241, ISSN: 2044-4753

The mechanism of ethylene trimerisation and tetramerisation with chromium–diphosphinoamine (Cr–PNP)catalysts has been studied by experimental and theoretical (DFT) methods. The effects of a pendant etherdonor (ortho-methoxyaryl ligand substitution) and of anion coordination to the active species have beenstudied. In the former case, coordination of the ether donor to chromium favours 1-hexene by suppressingformation of the bisIJethylene) chromacyclopentane intermediate which is postulated to be the major routeto 1-octene. The effect of anion coordination is similar and as the coordination strength increases, displacementof the anion by a second ethylene ligand becomes more difficult, again favouring trimerisationover tetramerisation. Hence, the experimentally observed effects of pendant donor coordination andchanges in anion coordination strength can be rationalised.

Journal article

Tomov AK, Nobbs JD, Chirinos JJ, Saini PK, Malinowski R, Ho SKY, Young CT, McGuinness DS, White AJP, Elsegood MRJ, Britovsek GJPet al., 2016, Alternating alpha-olefin distributions via single and double insertions in chromium-catalyzed ethylene oligomerization., Organometallics, Vol: 36, Pages: 510-522, ISSN: 0276-7333

The catalytic oligomerization of ethylene with chromium-based complexes containing bis(benzimidazolemethyl)amine (BIMA) ligands results in alternating distributions of linear α-olefins (LAOs). Extremely high activities are obtained (>100 000 g mmol–1 h–1 bar–1) with N-alkyl-substituted BIMA ligands, whereas bulky groups on the central nitrogen or alternative central donors result in much lower activities. Variations in the ligand backbone, as well as methylation of the benzimidazole units, lead to reduction in activity. The alternating LAO distributions have been mathematically analyzed using second-order recurrence relations. The shape of the distributions is affected by ethylene pressure (1–4 bar) and by the cocatalyst to some degree. On the basis of the results and analysis presented herein, we propose that the alternating behavior originates from the ability of these chromium BIMA catalysts to undergo single as well as double ethylene insertion reactions. A minor second distribution (<5 wt %) of 2-ethyl-1-alkenes is obtained under certain conditions, resulting from incorporation of 1-butene. DFT studies (M06L) and experimental observations regarding the reaction between AlMe3 and the N-methyl BIMA ligand 2 have shown that deprotonation of the benzimidazole N–H units can occur, which suggests a change in coordination of the BIMA ligand under oligomerization conditions.

Journal article

Britovsek GJ, McGuinness DS, 2016, A DFT mechanistic study on ethylene tri- and tetramerization with Cr/PNP catalysts: single versus double insertion pathways, Chemistry - A European Journal, Vol: 22, Pages: 16891-16896, ISSN: 0947-6539

The mechanism of ethylene trimerization and tetramerization with a chromium-diphosphinoamine (Cr-PNP) catalyst system has been studied by theoretical (DFT) methods. Two representative ligands have been explored, namely Ph2 PN(Me)PPh2 and (o-MeC6 H4 )2 PN(Me)P(o-MeC6 H4 )2 . Calculations on the former ligand reveal how a combination of single and double ethylene insertion mechanisms may lead to 1-hexene, 1-octene and the major side products (cyclopentanes and n-alkanes). For the latter ligand, introduction of o-alkyl substitution leads to a more sterically congested active species, which suppresses the available pathways for tetramerization and side product formation. Hence, the high selectivity of o-aryl substituted PNP ligands for trimerization can be rationalized.

Journal article

Petersen AR, White AJ, Britovsek GJ, 2016, Divergent reactivity of platinum(II) and palladium(II) methylperoxo complexes and the formation of an unusual hemi-aminal complex, Dalton Transactions, Vol: 45, Pages: 14520-14523, ISSN: 1477-9226

The 6,6′′-diaminoterpyridine palladium(II) methylperoxo complex eliminates methyl hydroperoxide and reacts with acetone to form a novel hemi-aminal palladium complex, whereas the analogous platinum(II) complex generates formaldehyde and a platinum(II) hydroxo complex.

Journal article

Martinez-Ferrate O, Lopez-Valbuena JM, Martinez Belmonte M, White AJP, Benet-Buchholz J, Britovsek GJP, Claver C, van Leeuwen PWNMet al., 2016, Novel iminopyridine derivatives: ligands for preparation of Fe(II) and Cu(II) dinuclear complexes, Dalton Transactions, Vol: 45, Pages: 3564-3576, ISSN: 1477-9226

A series of imino- and amino-pyridine ligands based on dihydrobenzofurobenzofuran (BFBF) and methanodibenzodioxocine (DBDOC) backbones have been synthesized. These ligands form exclusively dinuclear complexes with metals such as iron(II) and copper(II). The structures for complexes 15, 16, 18, 19, 20, 21, 23, and 24 were determined by X-ray crystallography. The complexes show large distances for the metal nuclei and different geometries depending on the nature of the metal. An octahedral geometry was observed for the iron(II) complexes, while copper(II) complex 24 showed a distorted trigonal bipyramidal geometry. The iron(II) complexes showed activity as catalysts in the cycloaddition of CO2 to epoxides, obtaining moderate yields of cyclic carbonates.

Journal article

Britovsek GJP, Malinowski R, McGuinness DS, Nobbs JD, Tomov AK, Wadsley AW, Young CTet al., 2015, Ethylene Oligomerisation Beyond Schulz-Flory Distributions, ACS Catalysis, Vol: 5, Pages: 6922-6925, ISSN: 2155-5435

The oligomerisation of ethylene producesα-olefin distributions ranging from Schulz-Flory distributionsto alternating and selective oligomer distributionswhich can be mathematically analysed and characterisedby recurrence relations.

Journal article

Britovsek GJP, McGuinness DS, Wierenga TS, Young CTet al., 2015, Single- and Double-Coordination Mechanism in Ethylene Tri- and Tetramerization with Cr/PNP Catalysts, ACS Catalysis, Vol: 5, Pages: 4152-4166, ISSN: 2155-5435

The mechanism of ethylene trimerization and tetramerization with a chromium–diphosphinoamine (Cr–PNP) catalyst system has been studied with combined experimental and theoretical methods. Of the total product output, 1-octene, cyclopentanes, n-alkanes, and higher (C10+) olefins are formed with a fractional (∼1.4) order response to ethylene concentration, whereas 1-hexene formation is approximately first-order in ethylene. Theoretical studies suggest a mechanism involving a cationic monometallic catalyst in Cr(I) and Cr(III) formal oxidation states. A key feature of the developed model is the occurrence of a double-coordination mechanism in which a bis(ethylene) chromacyclopentane intermediate is responsible for 1-octene formation as well as the other coproducts that have a greater than first-order response to ethylene. In contrast, 1-hexene is formed primarily from a mono(ethylene) chromacyclopentane intermediate. The selectivity of catalysis is governed by the competition between single- and double-coordination pathways. The mechanistic model developed displays excellent correlation with experimental observations and is able to fully explain the formation of all products generated with this catalyst.

Journal article

Britovsek GJP, Grau M, 2015, High-Valent Iron in Biomimetic Alkane Oxidation Catalysis, Iron Catalysis II, Editors: Bauer, Publisher: Springer, Pages: 145-172

Book chapter

Grau M, Britovsek GJP, 2015, High-Valent Iron in Biomimetic Alkane Oxidation Catalysis, IRON CATALYSIS II, Editors: Bauer, Publisher: SPRINGER-VERLAG BERLIN, Pages: 145-171, ISBN: 978-3-319-19395-3

Book chapter

Martínez-Ferraté O, Britovsek GJP, Claver C, van Leeuwen PWNMet al., 2015, C–H benzylic oxidation promoted by dinuclear iron DBDOC iminopyridine complexes, Inorganica Chimica Acta, ISSN: 0020-1693

Journal article

Petersen AR, Taylor RA, Vicente-Hernandez I, Mallender PR, Olley H, White AJP, Britovsek GJPet al., 2014, Oxygen insertion into metal carbon bonds: formation of methylperoxo Pd(II) and Pt(II) complexes via photogenerated dinuclear intermediates, Journal of the American Chemical Society, Vol: 136, Pages: 14089-14099, ISSN: 1520-5126

Platinum(II) and palladium(II) complexes [M(CH₃)(L)]SbF₆ with substituted terpyridine ligands L undergo light-driven oxygen insertion reactions into metal methyl bonds resulting in methylperoxo complexes [M(OOCH₃)(L)]SbF₆. The oxygen insertion reactions occur readily for complexes with methyl ligands that are activated due to steric interaction with substituents (NH₂, NHMe or CH₃) at the 6,6″-positions on the terpyridine ligand. All complexes exhibit attractive intermolecular π···π or M···M interactions in the solid state and in solution, which lead to excited triplet dinuclear M–M complexes upon irradiation. A mechanism is proposed whereby a dinuclear intermediate is generated upon irradiation that has a weakened M–C bond in the excited state, resulting in the observed oxygen insertion reactions.

Journal article

Cecchini MP, Turek VA, Demetriadou A, Britovsek G, Welton T, Kornyshev AA, Wilton-Ely JDET, Edel JBet al., 2014, Heavy Metal Sensing Using Self-Assembled Nanoparticles at a Liquid–Liquid Interface, Advanced Optical Materials

Journal article

Petersen AR, Taylor RA, Vicente-Hernandez I, Heinzer J, White AJP, Britovsek GJPet al., 2014, Light-Driven Methyl Exchange Reactions in Square-Planar Palladium(II) and Platinum(II) Complexes, ORGANOMETALLICS, Vol: 33, Pages: 1453-1461, ISSN: 0276-7333

Journal article

McGuinness DS, Chan B, Britovsek GJP, Yates BFet al., 2014, Ethylene Trimerisation with Cr-PNP Catalysts: A Theoretical Benchmarking Study and Assessment of Catalyst Oxidation State, AUSTRALIAN JOURNAL OF CHEMISTRY, Vol: 67, Pages: 1481-1490, ISSN: 0004-9425

Journal article

Grau M, Rigodanza F, White AJP, Soraru A, Carraro M, Bonchio M, Britovsek GJPet al., 2014, Ligand tuning of single-site manganese-based catalytic antioxidants with dual superoxide dismutase and catalase activity, CHEMICAL COMMUNICATIONS, Vol: 50, Pages: 4607-4609, ISSN: 1359-7345

Journal article

Grau M, Kyriacou A, Martinez FC, de Wispelaere IM, White AJP, Britovsek GJPet al., 2014, Unraveling the origins of catalyst degradation in non-heme iron-based alkane oxidation, DALTON TRANSACTIONS, Vol: 43, Pages: 17108-17119, ISSN: 1477-9226

Journal article

Grau M, England J, de Rosales RTM, Rzepa HS, White AJP, Britovsek GJPet al., 2013, Coordination Equilibria Between Seven- and Five-coordinate Iron(II) Complexes, INORGANIC CHEMISTRY, Vol: 52, Pages: 11867-11874, ISSN: 0020-1669

Journal article

Whiteoak CJ, Nobbs JD, Kiryushchenkov E, Pagano S, White AJP, Britovsek GJPet al., 2013, Tri(pyridylmethyl)phosphine: The Elusive Congener of TPA Shows Surprisingly Different Coordination Behavior, INORGANIC CHEMISTRY, Vol: 52, Pages: 7000-7009, ISSN: 0020-1669

Journal article

Coskun T, Conifer CM, Stevenson LC, Britovsek GJPet al., 2013, Carbodeoxygenation of Biomass: The Carbonylation of Glycerol and Higher Polyols to Monocarboxylic Acids, CHEMISTRY-A EUROPEAN JOURNAL, Vol: 19, Pages: 6840-6844, ISSN: 0947-6539

Journal article

Wong E, Jeck J, Grau M, White AJP, Britovsek GJPet al., 2013, A strong-field pentadentate ligand in iron-based alkane oxidation catalysis and implications for iron(IV) oxo intermediates, CATALYSIS SCIENCE & TECHNOLOGY, Vol: 3, Pages: 1116-1122, ISSN: 2044-4753

Journal article

Karpiniec SS, McGuinness DS, Britovsek GJP, Patel Jet al., 2012, Acetylene Cyclotrimerization with an Iron(II) Bis(imino)pyridine Catalyst, ORGANOMETALLICS, Vol: 31, Pages: 3439-3442, ISSN: 0276-7333

Journal article

Nobbs JD, Tomov AK, Cariou R, Gibson VC, White AJP, Britovsek GJPet al., 2012, Thio-Pybox and Thio-Phebox complexes of chromium, iron, cobalt and nickel and their application in ethylene and butadiene polymerisation catalysis., Dalton Trans., Vol: 41, Pages: 5949-5964, ISSN: 1477-9226

Seven bis(thiazolinyl)- and bis(thiazolyl)pyridine Thio-Pybox ligands and their metal complexes of Cr(III), Fe(II), Co(II) and Ni(II) were prepd., as well as a Ni(II) complex contg. a monoanionic bis(thiazolinyl)phenyl Thio-Phebox ligand. These new metal complexes were characterized and used as catalysts, in combination with the co-catalyst MAO, for the polymn. of ethylene and for the polymn. of butadiene. In the case of ethylene polymn., the Thio-Pybox and Thio-Phebox metal complexes showed relatively low polymn. activities, much lower compared to the related bis(imino)pyridine complexes of the same metals. In the polymn. of butadiene, several Thio-Pybox Co(II) complexes show very high activities, significantly higher than the other metal complexes with the same ligand. It is the metal, rather than the ligand, that appears to have the most profound effect on the catalytic activity in butadiene polymn., unlike in the polymn. of ethylene, where bis(imino)pyridine ligands provide highly active catalysts for a range of 1st row transition metals. The mol. structures of one ligand and eight complexes were detd. by x-ray crystallog. [on SciFinder(R)]

Journal article

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