ORCID Profile
0000-0003-2722-8534
Current Organisation
University of New South Wales
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Physical Organic Chemistry | Transport Properties and Non-Equilibrium Processes | Organic Chemistry | Medical Physics | Other Physical Sciences | Organic Chemical Synthesis | Condensed Matter Imaging
Expanding Knowledge in the Chemical Sciences | Expanding Knowledge in the Physical Sciences | Cancer and Related Disorders |
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C1FD00060H
Abstract: The effects on the rate and activation parameters of a series of Menschutkin processes on changing from a molecular solvent to an ionic liquid were investigated. The removal of delocalised pi-systems from the reagents does not affect the change in activation parameters on changing solvent. In each of the cases investigated, rate accelerations observed on moving to the ionic liquid could be attributed to an increase in reaction entropy. This suggests a specific interaction of the ionic liquid with the nucleophilic centre, rather than the delocalised pi-systems of either the electrophile or the nucleophile.
Publisher: Wiley
Date: 07-11-2018
Abstract: Molecular dynamics simulations of solutions of hexan-1-amine or 4-methoxybenzaldehyde in acetonitrile, an ionic liquid/acetonitrile mixture (χ
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8CP02527D
Abstract: NMR, thermoelectrochemical and Kamlet–Taft solvochromatic analyses provide insight into the coordination of lithium in both dilute and concentrated lithium–glyme solutions.
Publisher: Informa UK Limited
Date: 10-01-2004
Publisher: Elsevier BV
Date: 07-1998
Publisher: CSIRO Publishing
Date: 2011
DOI: 10.1071/CH11227
Abstract: A range of metal carbene complexes containing the ionic liquid-derived N-heterocyclic carbene (NHC) 1-nbutyl-3-methylimidazol-2-ylidene (IBuMe, 1) have been prepared by (i) direct ligand substitution using the free NHC ([Mo(CO)5(IBuMe)] 2), (ii) transmetallation using the silver salt [AgCl(IBuMe)] (3) ([RhCl(NBD)(IBuMe)] (4) and [IrCl(COD)(IBuMe)] (5), NBD = 2,5-norbornadiene, COD = 1,5-cyclooctadiene) and (iii) direct reaction of a metal acetate with the hydrochloride salt of 1 (trans-[PdCl2(IBuMe)] (6)). The dicarbonyl cis-[RhCl(CO)2(IBuMe)] (7) has been prepared by diene substitution under a carbon monoxide atmosphere. The molecular structures of 2, 4, 5 and 6 are reported and the sigma donation and steric properties of 1 are discussed relative to those of common imidazol-2-ylidene ligands.
Publisher: CSIRO Publishing
Date: 2015
DOI: 10.1071/CH14458
Abstract: A series of fluorous surfactants with additional functionality were generated through the attachment of substituents at the amino nitrogen atom of the surfactant moiety. Ex les of molecules containing one and two triazole ring systems were synthesized through N-alkylation and N-acylation strategies.
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4NJ90052A
Abstract: Correction for ‘The effect of an ionic liquid on the rate of reaction at a phosphorus centre' by Bradley J. Butler et al., New J. Chem. , 2015, DOI: 10.1039/c4nj01224k.
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7OB01096F
Abstract: An ionic liquid is used to facilitate ether cleavage without the presence of side reactions the microscopic origins of the solvent effects are examined. Controlled cleavage of this kind of ether is relevant in the fractionation of lignin.
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4NJ01224K
Abstract: Rate constant of a substitution at phosphorus varies with amount of ionic liquid present enthalpic benefit offsets entropic cost.
Publisher: Wiley
Date: 30-11-2021
Abstract: Electronic probes of ligands, particularly carbenes, are widely used in assessing electronic properties the results inform the selection of a ligand for a given application. As such, it is important to ensure the data obtained is reliable and unaffected by other factors, such as the steric bulk of the ligand. The effects of such steric factors on two commonly used electronic probes (based on palladium and selenium) are investigated here, with the selenium adduct found to be particularly sensitive. It is hoped that this serves as a cautionary tale to always critically evaluate what a probe is measuring.
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8SC03218A
Abstract: Surprisingly small structural changes in Donor–Acceptor Stenhouse Adducts (DASAs) result in predictable, robust and effective photochromic switches.
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5OB01214G
Abstract: An ionic liquid is shown to increase the rate of all three steps in this imine formation and the microscopic origins of such are investigated. The magnitude of this enhancement varies with the nature of the substituent, though in all cases the rate of imine formation is increased.
Publisher: Wiley
Date: 11-02-2020
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7OB01476G
Abstract: The nucleophilic aromatic substitution reaction between 1-fluoro-2,4-dinitrobenzene and ethanol was examined in a series of ionic liquids across a range of mole fractions.
Publisher: Wiley
Date: 03-09-2012
Abstract: The Group XIV tetratolyl series X(C(6)H(4)-CH(3))(4) (X = C, Si, Ge, Sn, Pb) were studied by using inelastic neutron scattering to measure the low-energy phonon spectra to directly access the methyl-group torsional modes. The effect of increased molecular radius as a function of the size of the central atom was shown to have direct influence on the methyl dynamics, reinforced with the findings of molecular dynamics and contact surface calculations, based upon the solid-state structures. The torsional modes in the lightest analogue were found to be predominantly intramolecular: the Si and Ge analogues have a high degree of intermolecular methyl-methyl group interactions, whilst the heaviest analogues (Sn and Pb) showed pronounced intermolecular methyl interactions with the whole phonon bath of the lattice modes.
Publisher: Wiley
Date: 31-03-2016
DOI: 10.1002/POC.3554
Publisher: American Chemical Society (ACS)
Date: 10-11-2021
Abstract: The nucleofugality of chloride has been measured in solvent mixtures containing ionic liquids for the first time, allowing reactivity in these solvents to be put in context with molecular solvents. Using well-described electrofuges, solvolysis rate constants were determined in mixtures containing different proportions of ethanol and the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide the different solvent effects observed as the mixture changed could be explained using interactions of the ionic liquid with species along the reaction coordinate, determined using temperature dependent kinetic studies. The solvolysis data allowed determination of the nucleofugality of chloride in these mixtures, which varied with the proportion of salt in the reaction mixture, demonstrating quantitatively the importance of the amount of ionic liquid in the reaction mixture in determining reaction outcome. Nucleofugality data for chloride were determined in seven further ionic liquids, with the reactivity shown to vary over more than an order of magnitude. This outcome illustrates that the components of the ionic liquid are critical in determining reaction outcome. Overall, this work quantitatively extends the understanding of solvent effects in ionic liquids and demonstrates the potential for such information to be used to rationally select an ionic liquid to control reaction outcome.
Publisher: Elsevier BV
Date: 07-2003
Publisher: American Chemical Society (ACS)
Date: 06-08-2021
Publisher: Elsevier BV
Date: 10-2007
Publisher: Wiley
Date: 12-01-2022
Abstract: The σ ‐donating and π ‐accepting properties of a series of N ‐methylimidazolium‐derived N ‐heterocyclic carbenes, systematically altered at the 4,5‐positions, were determined using two NMR‐based probe techniques. The sterically slight methyl substituent provided reliable probe data, free from through‐space effects, and reliable measures of the electronic properties. Correlations with established electronic parameters for the substituents show that the electronic properties of carbenes, when extraneous effects are controlled for, are indeed predictable. These correlations were compared with earlier data which revealed a previously unrecognised systematic deviation for N ‐aryl substituents.
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3RA42820F
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9OB01807G
Abstract: The effects of ionic liquids on the rate constant of an S N 1 process with a xanthylium intermediate differ from those observed for other S N 1 reactions. These effects can be correlated to solvent parameters of the ionic liquids allowing predictability.
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0OB01500H
Abstract: Bisimidazolium-based ionic liquids generally result in greater rate constants than the corresponding monocationic salts. The effect depends on the length of the bridging chain likely due to a change in the mode of interactions in solution.
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8OB00651B
Abstract: Variety of ionic liquids with different anions used as solvents for a nucleophilic aromatic substitution reaction.
Publisher: American Chemical Society (ACS)
Date: 09-07-2009
DOI: 10.1021/LA901526E
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C7FD90091K
Publisher: American Chemical Society (ACS)
Date: 27-07-2007
DOI: 10.1021/LA701035G
Publisher: Wiley
Date: 22-02-2019
DOI: 10.1002/POC.3819
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D0CP04227G
Abstract: Machine learning models were developed for an organic reaction in ionic liquids and validated on a selection of ionic liquids.
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/C0OB00306A
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3RA04302A
Abstract: The rate constant for ethanolysis of an acenapthyl chloride in mixtures containing ionic liquids is estimated, demonstrating the potential for quantitative prediction of ionic liquid solvent effects.
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/B923890P
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C1CC12082D
Abstract: Reaction profiles for a Mizoroki-Heck reaction in either an ionic liquid or a molecular solvent with different palladium sources demonstrate that the rate enhancements observed in ionic liquids cannot be solely attributed to Pd-carbene complex formation.
Publisher: CSIRO Publishing
Date: 2015
DOI: 10.1071/CH14117
Abstract: The effect of a series of ionic liquids containing different anions (bis(trifluoromethanesulfonyl)imide, dicyanimide, hexafluorophosphate, tetrafluoroborate, and bromide) on the rate constant of a bimolecular substitution process was investigated. A general ionic liquid effect was noted, with increases in the rate constant observed in all ionic liquids used when compared with that in acetonitrile. Temperature-dependent kinetic data allowed calculation of activation parameters in each of the reaction mixtures considered these parameters showed that the microscopic origins of the rate enhancements observed were not the same for all of the ionic liquids used, demonstrating the importance of the nature of the anion.
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8CC00241J
Abstract: Rational selection of ionic liquids to get the rate constant you want in a substitution process.
Publisher: Wiley
Date: 08-2010
Publisher: Wiley
Date: 05-12-2016
Publisher: Wiley
Date: 04-2009
DOI: 10.1002/MRC.2401
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D0CP06066F
Abstract: Rate coefficient and spin–spin relaxation time measurements are used to understand and predict solvent effects in ionic liquids.
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C1CP21450K
Publisher: Elsevier BV
Date: 06-2003
Publisher: Elsevier
Date: 2011
Publisher: IEEE
Date: 02-2010
Publisher: Wiley
Date: 27-05-2016
Abstract: Novel ionic liquids containing chlorine atoms on the imidazolium cation were synthesised. The physicochemical properties of these ionic liquids were investigated extensively, including glass transition, melting and decomposition temperatures, density, viscosity, miscibility with common solvents and electrochemical window. The behaviour of these ionic liquids as solvents was examined through temperature-dependent kinetic analyses on two reactions: a nucleophilic aromatic substitution (S
Publisher: Wiley
Date: 08-06-2010
Publisher: Royal Society of Chemistry (RSC)
Date: 2002
DOI: 10.1039/C5OB02598B
Abstract: An ionic liquid significantly increases benzylic carbocation formation due to favourable ionic liquid–transition state interactions. The magnitude of transition state solvation was shown to be critical, explaining the difference between this and previous cases.
Publisher: American Chemical Society (ACS)
Date: 04-02-2022
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2RA21889E
Publisher: Elsevier BV
Date: 11-2005
Publisher: Wiley
Date: 26-10-2016
Abstract: The self-diffusion coefficients of each component in mixtures of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Bmim][N(SO
Publisher: Wiley
Date: 29-06-2009
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1CP90187G
Abstract: This special cross-journal collection of Organic and Biomolecular Chemistry ( OBC ) and Physical Chemistry Chemical Physics ( PCCP ) is dedicated to non-traditional solvent effects in organic reactions.
Publisher: American Chemical Society (ACS)
Date: 11-08-2022
Abstract: This paper introduces an economical approach for improving the accuracy and convergence of quantum mechanics/molecular mechanics (QM/MM) models. The approach is tested on a series of neutral and charged amino acids embedded in a 160-water cluster, where their intramolecular proton transfer energies (neutral amino acid → zwitterionic amino acid) were previously obtained at the ωB97X-D/6-31G(d) level of theory. When the charges on the MM atoms were replaced with those obtained at the same QM level of theory used to treat the QM atoms, this significantly improved the accuracy and convergence of the QM/MM models. In particular, the QM/MM model converged to within 1.4 kcal mol
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5OB01215E
Abstract: Reactivity studies have been used to order a series of polycyclic aromatic hydrocarbons, demonstrating that the curved species corannulene has comparable reactivity to triphenylene.
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C1AN15693D
Abstract: A simple colorimetric method for the detection of copper ions in water is described. This method is based on the 'click' copper(I)-catalyzed azide-alkyne cycloaddition reaction and its use in promoting the aggregation of azide-tagged gold nanoparticles by a dialkyne cross-linker is described. Nanoparticle cross-linking, evidenced as a colour change, is used for the detection of copper ions. The lowest detected concentration by the naked eye was 1.8 μM, with the response linear with log(concentration) between 1.8-200 μM. The selectivity relative to other potentially interfering ions was evaluated.
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9OB02258A
Abstract: The effect of structure on the p K a value of triazolium salts in dimethyl sulfoxide is quantified, considering common structural and electronic motifs. Included is the first p K a measurement of a triazolium salt that generates a mesionic carbene.
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0OB01198C
Abstract: Using an ionic liquid in the solvent mixture for the reaction of a galactose substrate leads to changes in both the rate constant and the products as the solvent composition changes.
Publisher: Wiley
Date: 22-04-2021
DOI: 10.1002/POC.4217
Abstract: A unimolecular reaction that proceeds predominantly through a phenonium ion intermediate was investigated in mixtures of an ionic liquid and methanol. Varying the proportion of the ionic liquid in the reaction mixture led to an increase in the rate constant compared with methanol when very small amounts of ionic liquid were present in the reaction mixture and a decrease when higher proportions of the salt were present. Activation parameters determined for the process showed that the effect of changing the solvent composition on the rate constant was due to a key interaction between the ionic liquid and the transition state of the process, similar to other unimolecular processes. Analysis of the stereochemistry of the products demonstrated that the ionic liquid had no effect on either the ratio of the stereochemistry of the substitution products, or the ratio of the substitution and eliminations mechanisms occurring in solution.
Publisher: American Chemical Society (ACS)
Date: 20-10-2016
DOI: 10.1021/LA803710D
Publisher: American Chemical Society (ACS)
Date: 16-09-2022
Publisher: Wiley
Date: 02-02-2017
Abstract: Simple Cope and Claisen rearrangements were investigated in an ionic liquid and a range of molecular solvents through a series of kinetic studies. Analysis of the solvent effects on the Cope rearrangement of 3-phenyl-1,5-hexadiene indicated that a solvophobic effect was responsible for the observed rate enhancement in the ionic liquid, and that this was due to preferential solvation of the transition state. A similar solvophobic effect contributes to the ionic liquid solvent effect on the Claisen rearrangement of allyl vinyl ether, although the ability of the ionic liquid to stabilise the incipient charges in the transition state also likely contributes to the rate increase observed in the ionic liquid solvent. The activation parameter data suggest that in this case the ionic liquid was interacting with species along the reaction coordinate through general coulombic interactions (more acetonitrile-like) rather than through hydrogen-bonding interactions (less ethanol-like).
Publisher: Elsevier BV
Date: 03-2008
Publisher: Wiley
Date: 07-10-2014
DOI: 10.1002/MRC.4161
Abstract: In order to understand reaction outcomes in ionic liquids, it is crucial to be able to follow the progress of these reactions. This review highlights the advantages of NMR spectroscopy over other analytical techniques in following reaction progress in ionic liquids, particularly addressing the practical aspects of the methodology and highlighting the range of processes that can be readily followed. Copyright © 2014 John Wiley & Sons, Ltd.
Publisher: Wiley
Date: 03-07-2006
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3OB41038B
Abstract: The rate of reaction of a Menschutkin process in a range of ionic liquids with different cations was investigated, with temperature-dependent kinetic data giving access to activation parameters for the process in each solvent. These data, along with molecular dynamics simulations, demonstrate the importance of accessibility of the charged centre on the cation and that the key interactions are of a generalised electrostatic nature.
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4RA14676J
Abstract: The utility of using a combined experimental and computational approach for understanding ionic liquid media, and their effect on reaction outcome, is highlighted through a number of case studies.
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4OB02482F
Abstract: Predictable changes in the rate constant of a condensation reaction were seen as the solvent composition was varied. The cation–nucleophile interaction could be controlled in a predictable manner activation parameters varied linearly with the H-bond acceptor ability of the anions used.
Publisher: American Chemical Society (ACS)
Date: 06-12-2016
Abstract: The rate constant for the reaction between hexan-1-amine and 4-methoxybenzaldehyde was determined in ionic liquids containing an imidazolium cation. The effect on the rate constant of increasing the length of the alkyl substituent on the cation was examined in a number of ionic liquid/acetonitrile mixtures. In general it was found that there was no significant effect of changing the alkyl substituent on the rate constant of this process, suggesting that any nanodomains in these mixtures do not have a significant effect on the outcome of this process. A series of small-angle X-ray scattering and wide-angle X-ray scattering experiments were performed on mixtures of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Bmim][N(CF
Publisher: EDP Sciences
Date: 11-2011
DOI: 10.2113/GSSGFBULL.182.6.467
Abstract: The late stages of the Variscan orogeny in western and central Europe are characterized by the emplacement of numerous Carboniferous granitic intrusions. In the southern part of the Armorican massif, volcanic and plutonic rocks occur within the Carboniferous series of the Ancenis basin. Chemical analyses indicate that they belong to the same magmatic high-K calc-alkaline association of peraluminous composition, which likely derives from crustal melting of an igneous source. A LA-ICPMS U-Pb/zircon age of 319.3 ± 3.1 Ma dates, for the first time, this magmatic event and, by there, constrains the maximum age of both the end of the sedimentation and the northward tilting of the sediments in the Ancenis basin. This magmatic event is coeval with the sedimentation of the coal-bearing Namurian basins located along the Nort-sur-Erdre fault. These intrusions are interpreted as the feeding conduits of the volcano-sedimentary layers encountered in these basins. This would imply a minimal dextral displacement of ca. 20–25 km along the Nort-sur-Erdre fault.
Publisher: Elsevier BV
Date: 08-2010
Publisher: American Chemical Society (ACS)
Date: 03-07-2017
Abstract: A range of more than 25 imidazolium salts, chosen for their differing steric and electronic features, were prepared, and their pK
Publisher: American Chemical Society (ACS)
Date: 05-04-2013
DOI: 10.1021/LA400358E
Abstract: Supramolecular interactions between two surface modification species are explored to control the ratio and distribution of these species on the resultant surface. A binary mixture of aryl diazonium salts bearing oppositely charged para-substituents (either -SO3(-) or -N(+)(Me)3), which also reduce at different potentials, has been examined on glassy carbon surfaces using cyclic voltammetry and X-ray photoelectron spectroscopy (XPS). Striking features were observed: (1) the two aryl diazonium salts in the mixed solution undergo reductive adsorption at the same potential which is distinctively less negative than the potential required for the reduction of either of the two aryl diazonium salts alone (2) the surface ratio of the two phenyl derivatives is consistently 1:1 regardless of the ratio of the two aryl diazonium salts in the modification solutions. Homogeneous distribution of the two oppositely charged phenyl species on the modified surface has also been suggested by XPS survey spectra. Diffusion coefficient measurements by DOSY NMR and DFT based computation have indicated the association of the two aryl diazonium species in the solution, which has led to changes in the molecular orbital energies of the two species. This study highlights the potential of using intermolecular interactions to control the assembly of multicomponent thin layers.
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4OB01070A
Abstract: Predictions of the effects of the proportion and the components of an ionic liquid on the reaction rate are shown to correlate well with experimental results.
Publisher: Bentham Science Publishers Ltd.
Date: 08-2006
Publisher: Wiley
Date: 23-11-2010
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5OB01637A
Abstract: Fusion of benzhydrols to give fluorenols is found to not affect the electronic susceptibility of substitution reactions suggesting the antiaromaticity of the intermediate serves simply to slow the process.
Publisher: Walter de Gruyter GmbH
Date: 28-04-2013
Abstract: Ionic liquids are frequently touted as alternatives to traditional molecular solvents but are limited in their applicability as the outcome of reactions may be altered on moving from a molecular to an ionic solvent. This manuscript summarizes our progress towards a predictive framework through understanding how ionic solvents affect organic processes, with an emphasis on how these findings might be applied. Particularly, we will consider the importance of the mole fraction of the ionic liquid used, including some hitherto undisclosed results, as well as the importance of understanding the key interactions of the solvent with the components along the reaction coordinate.
Publisher: Wiley
Date: 22-06-2012
Abstract: Smart surfaces presenting both antifouling molecules with a charged functional group at their distal end, and molecules that are terminated by RGD peptides for cell adhesion, were fabricated and characterized (see picture). By applying potentials of +300 or -300 mV, the surfaces could be dynamically switched to make the peptide accessible or inaccessible to cells.
Publisher: MDPI AG
Date: 13-07-2009
Publisher: American Chemical Society (ACS)
Date: 04-10-2007
DOI: 10.1021/AR700065S
Publisher: American Chemical Society (ACS)
Date: 03-01-2018
Abstract: Structural modification of the tetrahydroisoquinoline (THIQ) framework is of significant interest to organic chemists due to its central role in heterocyclic and medicinal chemistry. Here we demonstrate an efficient metal-free method for the oxidative functionalization of THIQs at the C1 position, which is amenable to a erse range of C-C coupling reactions. These reactions proceed through a hydride abstraction involving the tropylium ion followed by quenching the generated iminium intermediates with nucleophiles to afford THIQ derivatives with excellent efficiencies and interesting selectivities.
Publisher: Wiley
Date: 13-06-2018
DOI: 10.1002/POC.3862
Publisher: Wiley
Date: 06-04-2018
Abstract: A range of lignin model compounds were examined for their reactivity with hydrogen bromide in the ionic liquid N-butylpyridinium triflate. It was found that the ionic liquid enabled rapid reaction at both the hydroxy and methyl ether sites of the model compounds at room temperature. Reactions at the phenyl ether moieties were more complex rather than facilitating cleavage at these sites, alternate breakdown products that had not been seen in previous studies were observed these products are consistent with functionalisation of the aromatic components of the model compounds.
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0OB00036A
Abstract: The effects of substitution, ring size and cyclisation on the p K a values of imidazolinium salts, higher homologues and formamidinium salts in DMSO are quantified, considering structural and electronic motifs along with crystallographic analyses.
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C8OB02460J
Abstract: The polarisability of an ionic liquid is key in determining the rate constant of a unimolecular substitution process.
Publisher: Wiley
Date: 07-2008
Publisher: Wiley
Date: 18-12-2007
Abstract: Silver(I) acetylides facilitate direct carbon–carbon bond formation at the bridgehead position of adamantane, and in some instances related systems such as carborate anions and bicyclo[2.2.2]octanes. Substrate constraints along with attempts to further understand the underlying mechanism are presented. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Publisher: Wiley
Date: 05-2019
Abstract: A series of nucleophiles containing Group 15 nucleophilic heteroatoms has been used to expand and develop the current understanding of ionic liquid solvent effects on bimolecular nucleophilic substitution processes. It was found that when using arsenic-, antimony- and bismuth-based nucleophiles, rate constant enhancement was observed for all solvent compositions containing ionic liquids. This rate constant enhancement was driven by ionic liquid/transition state interactions, which contrasts with previous studies on earlier Group 15 nucleophiles. This study provides a holistic understanding and augments the predictive framework for the effects of ionic liquids on bimolecular nucleophilic substitution processes, with the potential for these periodic trends to be broadly applied.
Publisher: American Chemical Society (ACS)
Date: 02-05-2008
DOI: 10.1021/LA800435D
Publisher: American Chemical Society (ACS)
Date: 04-01-2021
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9OB01753D
Abstract: The solvent effects of solvate ionic liquids have been compared to the effects of previously studied ‘typical’ ionic liquids for the S N 2 reaction between pyridine and benzyl bromide and the S N Ar reaction between ethanol and 1-fluoro-2,4-dinitrobenzene.
Publisher: Wiley
Date: 23-03-2023
Abstract: The self‐diffusion coefficients of each of the components in mixtures containing pyridine and each of the homologous series 1‐alkyl‐3‐methylimidazolium bis (trifluoromethanesulfonyl)imides in acetonitrile were determined using NMR diffusometry ( i. e ., Pulsed Gradient Spin Echo). The nature of solvation was found to change significantly with the proportion of salt in the mixtures. Increased diffusion coefficients (when corrected for viscosity) for the molecular components were observed with increasing proportion of ionic liquid and with increasing alkyl chain length on the cation. Comparison of the molecular solvents suggests increased interactions in solution of the pyridine with other components of the mixture, consistent with the proposed interactions shown previously to drive changes in reaction kinetics. Discontinuities were seen in the diffusion data for each species in solution across different ionic liquids between the hexyl and octyl derivatives, suggesting a change in the structuring in solution as the alkyl chain on the cation changes and demonstrating the importance of such when considering homologous series.
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6CC08079K
Abstract: We report photochromic donor–acceptor Stenhouse adducts (DASAs) capable of fully reversible photoisomerization with visible light in organic solvents including chloroform, acetonitrile and benzene.
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C8CP06701E
Abstract: Difference spectroscopy of functionalised ionic liquids can help resolve photoemission signals beyond that previously thought possible.
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2CC34074G
Abstract: A general 'one-pot' method for determining relative rates of reaction in complex mixtures has been established using free energy relationships to demonstrate its utility. Competition experiments involving as many as seven species gave relative rate constants that are in good agreement to those obtained from in idual kinetic analyses.
Publisher: Elsevier BV
Date: 10-2005
Publisher: American Chemical Society (ACS)
Date: 03-2005
DOI: 10.1021/OL050121+
Publisher: Wiley
Date: 25-06-2021
Abstract: The electronic properties of a series of imidazolium‐derived N ‐heterocyclic carbenes systematically substituted at the 4,5‐positions were investigated through NMR analysis of their palladium and selenone derivatives. This combined approach provided information on both the σ ‐donating ability and the π ‐accepting ability of the carbenes, allowing correlation with the electronic nature of the substituents on the carbene and providing an understanding of the structural features that affect these properties in principle, this allows design of related ligands with known electronic parameters. Along with a greater understanding of the electronic properties of this series of carbenes, the work allows a comparison of the utility of both NMR probes based on the information gained, and the differences in requirements for preparation and acquisition. With this in mind, the selenone probe is proposed as being able to provide a wide range of electronic information, along with being relatively easily prepared.
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3OB41634H
Abstract: The effect of a range of ionic liquids, with systematic variations in the cation and anion, on the rate constant of an aromatic substitution process was investigated. Temperature-dependent kinetic data allowed calculation of activation parameters for the process in each solvent. These data demonstrate a generalised ionic liquid effect, with an increase in rate constant observed in each ionic solvent, though the microscopic origins of the rate constant enhancement differ with the nature of the ionic liquid.
Publisher: Elsevier BV
Date: 03-2009
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6CC03771B
Abstract: N-Heterocyclic olefins (NHOs) chemically transfer the base from solid phase and promote alkylation reaction on a wide range of substrates.
Publisher: Informa UK Limited
Date: 20-09-2004
Publisher: Informa UK Limited
Date: 10-05-2004
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B909171H
Abstract: The effect on the rate of reaction of each of a series of Menschutkin processes on changing from a molecular solvent to an ionic liquid was investigated. In each case, the rate acceleration observed at room temperature could be attributed to the change in the entropy of the system on reaching the transition state, offsetting any enthalpic cost.
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4OB00492B
Abstract: Three novel analogues of the cyclic pentapeptide sansalvamide A have been synthesised in high yield. A leucine residue in the lead compound is replaced with either a glycine, β-alanine or GABA residue, and the corresponding linear precursor peptides are found to cyclise with dramatically improved efficiency. This correlates with an increase in the effective molarity (EM) of the cyclisation reactions.
Publisher: American Chemical Society (ACS)
Date: 24-12-2015
DOI: 10.1021/ED400701M
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0CP04224B
Abstract: An iterative, combined experimental and computational approach towards predicting reaction rate constants in ionic liquids is presented.
Publisher: CSIRO Publishing
Date: 1995
DOI: 10.1071/CH9951379
Abstract: From intermolecular and intramolecular competition experiments, it has been established that, by comparison with an N-methyl substituent, an N-acetyl group deactivates glycine residues in piperazine-2,5-diones towards free-radical bromination. Combined with the ease of introduction and removal of N-acetyl substituents, the deactivating effect provides a method for regiocontrolled functionalization of these compounds.
Publisher: Wiley
Date: 22-08-2017
Publisher: Wiley
Date: 12-2018
Abstract: Bimolecular nucleophilic substitution reactions between triphenylphosphine and benzylic electrophiles have been examined in an ionic liquid to probe interactions with species along the reaction coordinate. Trends in the rate constant were found on both varying the leaving group and the electronic nature of the aromatic ring. In all the cases considered, interactions between the components of the ionic liquid and the transition state were shown to be more significant in determining reaction outcome than previously observed for this class of reaction. This demonstrates the importance of considering interactions of the ionic liquid components with all species along the reaction coordinate when investigating the origin of ionic liquid solvent effects, along with how such effects might be exploited.
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B805255G
Abstract: Temperature dependent rate studies demonstrate an enthalpic benefit and an entropic cost associated with the change in the rate of a unimolecular substitution process on addition of a high proportion of an ionic liquid, the latter effect being supported by molecular dynamics simulations.
Publisher: IEEE
Date: 02-2010
Publisher: Wiley
Date: 05-2019
Abstract: Nucleophilic aromatic substitution (S
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B705571D
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/B919831H
Abstract: Aromatic substitution of 1-fluoro-2,4-dinitrobenzene has been shown to proceed more rapidly in an ionic liquid than in ethanol, primarily due to entropic, rather than enthalpic, effects. By using molecular dynamics simulations, an anion-pi interaction appears to contribute to strong ordering within the starting material complex that accounts for the relative differences in the S(N)Ar k.
Location: United Kingdom of Great Britain and Northern Ireland
Start Date: 2013
End Date: 12-2016
Amount: $360,000.00
Funder: Australian Research Council
View Funded ActivityStart Date: 2018
End Date: 12-2023
Amount: $408,636.00
Funder: Australian Research Council
View Funded ActivityStart Date: 05-2014
End Date: 05-2015
Amount: $1,064,000.00
Funder: Australian Research Council
View Funded Activity