School of Chemistry - Research Publications
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ItemNo Preview AvailableLiberation of carbon monoxide from formic acid mediated by molybdenum oxyanions(ROYAL SOC CHEMISTRY, 2023-11-07)Multistage mass spectrometry experiments, isotope labelling and DFT calculations were used to explore whether selective decarbonylation of formic acid could be mediated by molybdate anions [(MoO3)x(OH)]- (x = 1 and 2) via a formal catalytic cycle involving two steps. In step 1, both molybdate anions undergo gas-phase ion-molecule reactions (IMR) with formic acid to produce the coordinated formates [(MoO3)x(O2CH)]- and H2O. In step 2, both coordinated formates [(MoO3)x(O2CH)]- undergo decarbonylation under collision-induced dissociation (CID) conditions to reform the molybdate anions [(MoO3)x(OH)]- (x = 1 and 2), thus closing a formal catalytic cycle. In the case of [MoO3(O2CH)]- an additional decarboxylation channel also occurs to yield [MoO3(H)]-, which is unreactive towards formic acid. The reaction between [Mo18O3(18OH)]- and formic acid gives rise to [Mo18O3(O2CH)]- highlighting that ligand substitution occurs without 18O/16O exchange between the coordinated 18OH ligand and HC16O2H. The reaction between [(MoO3)x(OD)]- (x = 1 and 2) and DCO2H initially produces [(MoO3)x(OH)]- (x = 1 and 2), indicating that D/H exchange occurs. DFT calculations were carried out to investigate the reaction mechanisms and energetics associated with both steps of the formal catalytic cycle and to better understand the competition between decarbonylation and decarboxylation, which is crucial in developing a selective catalyst. The CO and CO2 loss channels from the monomolybdate anion [MoO3(O2CH)]- have similar barrier heights which is in agreement with experimental results where both fragmentation channels are observed. In contrast, the dimolybdate anion is more selective, since the decarbonylation pathway of [(MoO3)2(O2CH)]- is both kinetically and thermodynamically favoured, which agrees with experimental observations where the CO loss channel is solely observed.
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ItemDifferentiation of aminohydroxypropanesulfonic acid structural isomers using tandem mass spectrometry-based methods(Elsevier BV, 2023-09)D-Cysteinolic acid (D-CA) is an important metabolite within the biosulfur cycle. A structural isomer, (R)-3-amino-2-hydroxypropanesulfonate ((R)-AHPS), is less common in nature but potentially can be misidentified as D-CA due to their many shared physical properties. To support confident assignment of these two isomers by use of mass spectrometry alone, this study explores the fragmentation reactions of their [M + H]+ and [M - H]- ions using collision-induced dissociation (CID). Electrospray ionization mass spectrometry (ESI-MS) experiments were conducted on authentic standards using an ion trap mass spectrometer, while a triple-quadrupole (QqQ) mass spectrometer was used in the selective reaction monitoring (SRM) mode to record energy-resolved CID. Density-functional theory (DFT) calculations were carried out at the M06/6-31+G* level of theory to study gas-phase fragmentation mechanisms. The data generated revealed kinetically-controlled fragmentations involving participation of neighboring amino groups in the positive ion mode. Negative ion mode MS analysis could distinguish the structural isomers through different collision energy-resolved results for m/z 95 product ions, CH3SO3−. DFT calculations revealed an enthalpy (ΔH) (Gibbs energy (ΔG)) gap of 31.8 (31.4) kJ/mol between transition state barriers of a concerted mechanism for D-CA, and a more preferred stepwise mechanism for (R)-AHPS.
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ItemNo Preview AvailableIon-pairs as a gateway to transmetalation: aryl transfer from boron to nickel and magnesium(ROYAL SOC CHEMISTRY, 2022-04-05)Gas-phase ion-ion reactions between tris-1,10-phenantholine metal dications, [(phen)3M]2+ (where M = Ni and Mg), and the tetraphenylborate anion yield the ion-pairs {[(phen)3M]2+[BPh4]-}+. The ion-pairs undergo transmetalation upon loss of a phen ligand to give the organometallic complexes [(phen)2M(Ph)]+. DFT calculations, used to determine the energy barriers for the transmetalation reactions and the hydrolysis reactions, are entirely consistent with the experimental results.
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ItemNo Preview AvailableNear thermal, selective liberation of hydrogen from formic acid catalysed by copper hydride ate complexes(ROYAL SOC CHEMISTRY, 2023-02-07)A near thermal two-step catalytic cycle for the selective release of hydrogen from formic acid by mononuclear cuprate anions was revealed using multistage mass spectrometry experiments, deuterium labelling and DFT calculations. In gas-phase ion-molecule reactions, mononuclear copper hydride anions [(L)Cu(H)]- (where L = H-, O2CH-, BH4- and CN-) were found to react with formic acid (HCO2H) to yield [(L)Cu(O2CH)]- and H2. The copper formate anions [(L)Cu(O2CH)]- can decarboxylate via collision-induced dissociation (CID) to reform the copper hydride [(L)Cu(H)]-, thereby closing the two-step catalytic cycle. Analogous labelling experiments with d1-formic acid (DCO2H) reveal that the decarboxylation process also occurs spontaneously. A kinetic study was carried out to provide further insights into the species involved in this reaction. Energetics from density functional theory (DFT) calculations show that the key decarboxylation step can occur without CID, thus in support of experimental observations.
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ItemNo Preview AvailableElectrospray Ionization Tandem Mass Spectrometry and DFT Survey of Copper(I) Ate Complexes Containing Coordinated Borohydride Anions(AMER CHEMICAL SOC, 2022-08-03)Copper(I) borohydride ate complexes of the type Cat+[XCu(BH4)]- have been previously postulated as intermediates in the reactions of copper salts with borohydride. Negative ion electrospray ionization of an acetonitrile solution of copper(I) phenylacetylide with a 10-fold excess of sodium borohydride (NaBH4) revealed the formation of a diverse range of mononuclear, dinuclear and trinuclear cuprates with different numbers of BH4-, H- and CN- ligands, the latter likely being formed by abstraction of CN- from the acetonitrile solvent. Collision-induced dissociation was used to examine the fragmentation reactions of the following borohydride containing cuprates: [Cu(H)(BH4)]-, [Cu(BH4)2]-, [Cu(BH4)(CN)]-, [Cu2(H)(BH4)2]-, [Cu2(H)2(BH4)]-, [Cu2(BH4)2(CN)]-, [Cu2(H)(BH4)(CN)]-, [Cu3(H)(BH4)3]-, [Cu3(H)2(BH4)2]-, [Cu3(H)3(BH4)]-, [Cu3(BH4)2(CN)2]-, and [Cu3(H)(BH4)2(CN)]-. In all cases, BH3 loss is observed. For many of the dinuclear and trinuclear complexes cluster fragmentation by loss of CuH was also observed. In the case of [Cu2(H)2(BH4)]- and [Cu3(H)3(BH4)]-, loss of H2 was also observed. DFT calculations were used to explore potential structures of the various borohydride-containing cuprates and to predict the overall reaction energetics for the various fragmentation channels.
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ItemNo Preview AvailableCatalytic Dehydrogenation of Liquid Organic Hydrogen Carrier Model Compounds by CpM+ (M = Fe, Co, Ni) in the Gas Phase(AMER CHEMICAL SOC, 2022-12-26)
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ItemElectronic and Steric Effects on the Reactivity of Seleniranium Ions with Alkenes in the Gas Phase(AMER CHEMICAL SOC, 2023-01-27)Gas phase ion-molecule reactions between seleniranium ions, R-c-SeCH2CH2+, and cis-cyclooctene were used to probe electronic and steric effects of substituents on kinetics and branching ratios. The second-order rate coefficients increased in the order p-OMeC6H4 < C6H5 < p-BrC6H4 < p-CF3C6H4 < m-NO2C6H4, giving a Hammett plot with R2 = 0.98 and ρ = +1.66. The two main pathways include direct transfer of the selenium moiety to the incoming alkene (π-ligand exchange) and the less favored ring-opening by attack at an iranium carbon to give a cis-bicyclic selenonium ion as supported by density functional theory (DFT) calculations. Branching ratios of each pathway indicated that electron-withdrawing groups directed more attack at carbon than selenium in agreement with previous solution-phase results. Increased steric bulk on selenium was investigated by changing the R group from a methyl to t-butyl, which not only shut down π-ligand exchange but also significantly reduced the overall reactivity. Finally, the reactivity of the iranium ion derived from Se-methylselenocysteine was investigated and shown to react faster and favor π-ligand exchange as the leaving group was changed from ethene to acrylic acid.
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ItemNo Preview AvailableBringing a Mechanistic Lens to the Development of New Transfer Hydroarylation Isodesmic Reactions for the Synthesis of Amides, Thioamides, Amidines, Alkenes and Ketones from Carboxylic Acids via Extrusion and Insertion Elementary Steps(Wiley, 2023-08-01)Abstract The wide availability, ease of handling and structural and functional diversity make carboxylic acids prized building blocks in organic synthesis. The past two decades has seen an explosion of interest in the development of new modes of reactivity of carboxylic acids and their derivatives. Of these, metal‐mediated decarboxylation reactions are attractive as they produce organometallic intermediates that can subsequently be used in C−X (where X=C, N, S etc) bond coupling reactions. Here the results of mechanistic studies integrating both gas‐ and condensed‐phase work are described for development of new extrusion‐insertion (ExIn) classes of reactions for the synthesis of amides, thioamides, amidines, alkenes and ketones from arylcarboxylic acids and suitable (hetero)cumulenes.
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ItemAromatic residues in the C-terminal helix of human apoC-I mediate phospholipid interactions and particle morphology(ELSEVIER, 2009-07)Human apolipoprotein C-I (apoC-I) is an exchangeable apolipoprotein that binds to lipoprotein particles in vivo. In this study, we employed a LC-MS/MS assay to demonstrate that residues 38-51 of apoC-I are significantly protected from proteolysis in the presence of 1,2-dimyristoyl-3-sn-glycero-phosphocholine (DMPC). This suggests that the key lipid-binding determinants of apoC-I are located in the C-terminal region, which includes F42 and F46. To test this, we generated site-directed mutants substituting F42 and F46 for glycine or alanine. In contrast to wild-type apoC-I (WT), which binds DMPC vesicles with an apparent Kd [Kd(app)] of 0.89 microM, apoC-I(F42A) and apoC-I(F46A) possess 2-fold weaker affinities for DMPC with Kd(app) of 1.52 microM and 1.58 microM, respectively. However, apoC-I(F46G), apoC-I(F42A/F46A), apoC-I(F42G), and apoC-I(F42G/F46G) bind significantly weaker to DMPC with Kd(app) of 2.24 microM, 3.07 microM, 4.24 microM, and 10.1 microM, respectively. Sedimentation velocity studies subsequently show that the protein/DMPC complexes formed by these apoC-I mutants sediment at 6.5S, 6.7S, 6.5S, and 8.0S, respectively. This is compared with 5.0S for WT apoC-I, suggesting the shape of the particles was different. Transmission electron microscopy confirmed this assertion, demonstrating that WT forms discoidal complexes with a length-to-width ratio of 2.57, compared with 1.92, 2.01, 2.16, and 1.75 for apoC-I(F42G), apoC-I(F46G), apoC-I(F42A/F46A), and apoC-I(F42G/F46G), respectively. Our study demonstrates that the C-terminal amphipathic alpha-helix of human apoC-I contains the major lipid-binding determinants, including important aromatic residues F42 and F46, which we show play a critical role in stabilizing the structure of apoC-I, mediating phospholipid interactions, and promoting discoidal particle morphology.