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Damien M Murphy

Publications and source records attributed to Damien M Murphy.

15 recordsLinked to original sources
PubMed2007

Free-radical pathways in the decomposition of ketones over polycrystalline TiO(2): the role of organoperoxy radicals.

The oxidative decomposition of various ketones (including acetone, 2-butanone, 4-heptanone, cyclopentanone and cyclohexanone) over dehydrated TiO(2) (P25) powder is investigated by electron paramagnetic resonance (EPR) spectroscopy. For the first time, a series of thermally unstable radical intermediates are observed both on the activated and reduced TiO(2) surface, depending on the adopted experimental conditions. These radical intermediates are identified as organoperoxy-based species of general formula ROO(.-) and RCO(3) (.-). They are formed by reaction of photogenerated charge carriers (either trapped electrons or trapped holes) with the adsorbed ketones in the presence of molecular oxygen. The organoperoxy intermediates are thermally unstable and decompose at temperatures in the region of 180-250 K. This work demonstrates that free-radical pathways involving both organoperoxy and superoxide radicals can be responsible for the thermal- and photodecomposition of ketones over polycrystalline TiO(2) (P25).

Journal Article↗
PubMed2006

Chemically induced fast solid-state transitions of omega-VOPO4 in vanadium phosphate catalysts.

Vanadium phosphates are important catalysts for the oxidation of alkanes, and commercial catalysts comprise a complex range of V4+ and V5+ phosphates. We used three complementary in situ characterization methodologies-powder x-ray diffraction and laser Raman and electron paramagnetic resonance spectroscopies-to show that the metastable phase omega-VOPO4 is very sensitive to many of the reactants and products of butane oxidation. A rapid transformation from omega-VOPO4 to delta-VOPO4 occurs on exposure to butane at the reaction temperature, and hence the metastable omega-VOPO4 may play a role in the formation of commercial catalysts.

Journal Article↗
PubMed2006

Principles and applications of ENDOR spectroscopy for structure determination in solution and disordered matrices.

Both electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) spectroscopies are extremely powerful and versatile methods for the characterisation of paramagnetic systems in biology, chemistry, and physics. However, by comparison to EPR, ENDOR remains a less widely used technique. In this tutorial review the basic principles of continuous wave ENDOR are described. The theory of orientation selective ENDOR, for structure determination in frozen solutions and powders, is then described. A range of examples, illustrating the type of information obtained from the ENDOR spectrum, is finally presented.

Electron Spin Resonance Spectroscopy↗
PubMed2006

An EPR, ENDOR and EIE study of gamma-irradiated poly (lactide-co-glycolide) polymers.

Gamma radiation of poly (lactide-co-glycolide) raw polymers and processed microspheres under vacuum and at 77 K results in the formation of a series of free radicals. The resulting powder electron paramagnetic resonance (EPR) spectrum contains a distribution of several different radicals, depending on the annealing temperature, and is therefore difficult to interpret. By utilising the selectivity of the electron nuclear DOuble resonance (ENDOR) and associated ENDOR induced EPR (EIE) techniques, a more direct approach for the deconvolution of the EPR spectrum can be achieved. Using this approach, the radiolytically induced CH3 *CHC(O)R- chain scission radical was identified at 120 K by simulation of the EIE spectrum. At elevated temperatures (250 K), this radical decays considerably and the more stable radicals -O*CHC(O)-, CH3 *C(OR)C(O)- and CH3 *C(OH)C(O)- predominate. This work demonstrates the utility of the EIE approach to supplement and aid the interpretation of powder EPR spectra of radicals in a polymer matrix.

Electron Spin Resonance Spectroscopy↗
PubMed2006

Excess electrons stabilized on ionic oxide surfaces.

Surface excess electrons are remarkable chemical entities that provide great opportunities for the design of new materials with precisely tuned electronic and magnetic properties. In this Account, we describe the structure and electronic properties of excess electron centers generated at the surface of insulating oxides. We also outline the elementary mechanisms that are at the basis of the generation of excess electrons at solid surfaces, setting a comparison to the general problem of excess electron localization in condensed media. Emphasis is given to morphological aspects relative to the surface-trapping sites as deduced from combined electron paramagnetic resonance and accurate quantum chemical calculations. The remarkable reactivity featured by the so formed "electron-rich" surfaces is illustrated, describing the reduction of simple diatomic molecules that form adsorbed radical anions via direct surface to adsorbate electron transfer.

Journal Article↗
PubMed2005

An EPR and ENDOR study of gamma- and beta-radiation sterilization in poly (lactide-co-glycolide) polymers and microspheres.

EPR/ENDOR spectroscopy was used to characterise the free radicals generated in a series of PLGA raw polymers and microspheres (with lactide:glycolide compositions of (75:25), (65:35) and (50:50)) after exposure to gamma (gamma-) and electron beam (beta-) irradiation at room temperature. Both sets of irradiated samples produced analogous EPR spectra, indicating that the type and distribution of free radicals generated by gamma-irradiation are similar to those generated by beta-irradiation. The radicals were identified by EPR simulations as the chain scission species -(CHO-(approximately 27% abundance),-C(CH(3))O- ( approximately 23% abundance) and the terminal-C(CH(3))-OR fragment (approximately 50% abundance), and these assignments were supported by the ENDOR analysis. The latter two radical species were demonstrated to originate from the lactide component of the PLGA polymer. Overall systematically higher radical concentrations were found as the lactide content of the PLGA raw polymer and microspheres increases (ie., 75:25 > 65:35 > 50:50) for both gamma- and beta-irradiation. However, while the relative concentrations of free radicals was similar in the raw polymer samples after exposure to gamma- or beta-irradiation, a substantial difference was found for the microsphere samples; an approximate doubling of the radical content was found in the gamma-irradiated PLGA microspheres compared to the identical beta-irradiated microspheres.

Beta Particles↗
PubMed2005

The reactivity of gallium-(I), -(II) and -(III) heterocycles towards Group 15 substrates: attempts to prepare gallium-terminal pnictinidene complexes.

The reactivity of a series of Ga(I), Ga(II) and Ga(III) heterocyclic compounds towards a number of Group 15 substrates has been investigated with a view to prepare examples of gallium-terminal pnictinidene complexes. Although no examples of such complexes were isolated, a number of novel complexes have been prepared. The reactions of the gallium(I) N-heterocyclic carbene analogue, [K(tmeda)][:Ga{[N(Ar)C(H)](2)}] (Ar = 2,6-diisopropylphenyl) with cyclo-(PPh)(5) and PhN[double bond, length as m-dash]NPh led to the unusual anionic spirocyclic complexes, [{kappa(2)P,P'-(PhP)(4)}Ga{[N(Ar)C(H)](2)}](-) and [{kappa(2)N,C-PhNN(H)(C(6)H(4))}Ga{[N(Ar)C(H)](2)}](-), via formal reductions of the Group 15 substrate. The reaction of the digallane(4), [Ga{[N(Ar)C(H)](2)}](2), with (Me(3)Si)N(3) afforded the paramagnetic, dimeric imido-gallane complex, [{[N(Ar)C(H) ](2)}Ga{mu-N(SiMe(3))}](2), via a Ga-Ga bond insertion process. In addition, the new gallium(III) phosphide, [GaI{P(H)Mes*}{[N(Ar)C(H)](2) }], Mes* = C(6)H(2)Bu(t)(3)-2,4,6; was prepared and treated with diazabicycloundecane (DBU) to give [Ga(DBU){P(H)Mes*}{[N(Ar)C(H)](2)}], presumably via a gallium-terminal phosphinidene intermediate, [Ga{[double bond, length as m-dash]PMes*}{[N(Ar)C(H)](2) }]. The possible mechanisms of all reactions are discussed, all new complexes have been crystallographically characterised and all paramagnetic complexes have been studied by ENDOR and/or EPR spectroscopy.

Journal Article↗
PubMed2005

EPR studies on the thiophenodithiazolyl radical, C4H2S3N.

Selective chlorination of thiophene-2,3-dithiol with SO(2)Cl(2) generates the corresponding sulfenyl chloride, 2,3-C(4)H(2)S(SCl)(2). Subsequent condensation with Me(3)SiN(3) yields the thiophenodithiazolylium salt [C(4)H(2)S(3)N]Cl, [TDTA]Cl. The structure of the cation, TDTA+, was established by X-ray diffraction as both its AsF(6)(-) and HSO(4)(-) salts. Reduction of [TDTA]Cl with Ag powder yields the radical TDTA* which was characterised by X- and Q-band (9 and 34 GHz) EPR and ENDOR studies. The spin density distributions estimated from the EPR/ENDOR measurements were found to be in very good agreement with those determined by DFT (B3LYP/6-31G*) indicating that ca 10% of the spin density is delocalised onto the thiophene ring. Comparison of the spin density distributions in TDTA* and the isoelectronic trithiatriazapentalenyl radical C(2)S(3)N(3), TTTA*, indicates that replacement of N by C-H leads to a localisation of the spin density on the dithiazolyl ring.

Journal Article↗
PubMed2005

An EPR and ENDOR investigation of a series of diazabutadiene-group 13 complexes.

Paramagnetic diazabutadienegallium(II or III) complexes, [(Ar-DAB)2Ga] and [{(Ar-DAB*)GaX}2] (X = Br or I; Ar-DAB = {N(Ar)C(H)}2, Ar = 2,6-diisopropylphenyl), have been prepared by reactions of an anionic gallium N-heterocyclic carbene analogue, [K(tmeda)][:Ga(Ar-DAB)], with either "GaI" or [MoBr2(CO)2(PPh3)2]. A related InIII complex, [(Ar-DAB*)InCl2(thf)], has also been prepared. These compounds were characterised by X-ray crystallography and EPR/ENDOR spectroscopy. The EPR spectra of all metal(III) complexes incorporating the Ar-DAB ligand, [(Ar-DAB(.))MX(2)(thf)(n)] (M = Al, Ga or In; X = Cl or I; n = 0 or 1) and [(Ar-DAB)2Ga], confirmed that the unpaired spin density is primarily ligand centred, with weak hyperfine couplings to Al (a = 2.85 G), Ga (a = 17-25 G) or In (a = 26.1 G) nuclei. Changing the N substituents of the diazabutadiene ligand to tert-butyl groups in the gallium complex, [(tBu-DAB*)GaI2] (tBu-DAB={N(tBu)C(H)}2), changes the unpaired electron spin distribution producing 1H and 14N couplings of 1.4 G and 8.62 G, while the aryl-substituted complex, [(Ar-DAB*)GaI2], produces couplings of about 5.0 G. These variations were also manifested in the gallium couplings, namely aGa approximately 1.4 G for [(tBu-DAB*)GaI2] and aGa approximately 25 G for [(Ar-DAB*)GaI2]. The EPR spectra of the gallium(II) and indium(II) diradical complexes, [{(Ar-DAB*)GaBr}2], [{(Ar-DAB*)GaI}2], [{(tBu-DAB*)GaI}2] and [{(Ar-DAB*)InCl}2], revealed doublet ground states, indicating that the Ga-Ga and In-In bonds prevent dipole-dipole coupling of the two unpaired electrons. The EPR spectrum of the previously reported complex, [(Ar-BIAN*)GaI2] (Ar-BIAN = bis(2,6-diisopropylphenylimino)acenaphthene) is also described. The hyperfine tensors for the imine protons, and the aryl and tert-butyl protons were obtained by ENDOR spectroscopy. In [(Ar-DAB*)GaI2], gallium hyperfine and quadrupolar couplings were detected for the first time.

Journal Article↗
PubMed2005

Reactions of a gallium(II)-diazabutadiene dimer, [{{[(H)C(Bu(t))N]2}GaI}2], with [ME(SiMe3)2] (M = Li or Na; E = N, P, or As): structural, EPR, and ENDOR characterization of paramagnetic gallium(III) pnictide complexes.

The reactions of the paramagnetic gallium(II) complex [{(Bu(t)-DAB)GaI}2] (Bu(t)-DAB = {(Bu(t))NC(H)}2) with the alkali metal pnictides [ME(SiMe3)2] (M = Li or Na; E = N, P, or As) have been carried out under a range of stoichiometries. The 1:2 reactions have led to a series of paramagnetic gallium(III)-pnictide complexes, [(Bu(t)-DAB)Ga{E(SiMe3)2}I] (E = N, P, or As), while two of the 1:4 reactions afforded [(Bu(t)-DAB)Ga{E(SiMe3)2}2] (E = P or As). In contrast, treatment of [{(Bu(t)-DAB)GaI}2] with 4 equiv of [NaN(SiMe3)2] resulted in a novel gallium heterocycle coupling reaction and the formation of the diradical species [(Bu(t)-DAB)Ga{N(SiMe3)2}{[CC(H)N2(Bu(t))2]Ga[N(SiMe3)2]CH3}]. The mechanism of this unusual reaction has been explored, and evidence suggests it involves an intramolecular transmethylation reaction. The X-ray crystal structures of all prepared complexes are reported, and all have been characterized by EPR and ENDOR spectroscopies. The observed spin Hamiltonian parameters provide a detailed picture of the distribution of the unpaired spin density over the molecular frameworks of the complexes.

Journal Article↗
PubMed2005

Evidence for the first oxidative insertion of a transition metal into a digallane(4): synthesis, structural characterisation and EPR studies of [Cp2Zr(III){Ga[N(Ar)C(H)]2}2][Li(THF)4], Ar = C6H3Pr(i)2-2,6.

Treatment of "ZrCp2" with the digallane(4), [{Ga[N(Ar)C(H)]2}2], Ar = C6H3Pri2-2,6, in the presence of excess Bu(n)Li leads to the first example of a gallyl-Group 4 complex, [Cp2Zr{Ga[N(Ar)C(H)]2}2][Li(THF)4], via an unprecedented oxidative insertion reaction; the paramagnetic complex has been characterised by X-ray crystallography and EPR spectroscopy.

Journal Article↗
PubMed2004

Direct observation of enantiomer discrimination of epoxides by chiral salen complexes using ENDOR.

Electron nuclear double resonance (ENDOR) spectroscopy was used to investigate the weak enantioselective binding between chiral salen complexes [VO(1)] ((R,R)- and (S,S)-vanadyl N,N'-bis(3,5-di-tert-butylsalcylidene)-1,2-cyclohexanediamine) and chiral epoxides (e.g., (R)-/(S)-propylene epoxide, 5) in frozen (10 K) solution. Differences in epoxide binding by enatiomers of [VO(1)] was evidenced by changes to the 1H epoxide derived peaks in the ENDOR spectra, such that (R,R)-[VO(1)] + (R)-5 and (R,R)-[VO(1)] + (S)-5 yield noticeably different spectra. These changes were assigned to the small structural differences between the diastereomeric metal-epoxide adducts. Simulation of the spectra revealed differences in the VO...1Hepoxide distances for the diastereomeric pairs, which was confirmed by a complementary set of density functional theory (DFT) calculations. While the epoxide molecule is very weakly coordinated, ENDOR measurements of the racemic complex in racemic epoxide nevertheless indicated the preferential coordination of the (R)-5 to (R,R)-[VO(1)] (likewise (S)-(5) to (S,S)-[VO(1)]), which is favored over the binding of (S)-5 epoxide to (R,R)-[VO(1)] (and likewise (R)-5 epoxide to (S,S)-[VO(1)]). This demonstrates the unique power of the ENDOR technique to resolve weak chiral interactions for which EPR spectroscopy alone lacks sufficient resolution.

Journal Article↗
PubMed2003

Electron magnetic resonance study of gamma-irradiated poly(lactide-co-glycolide) microspheres.

A series of poly(lactide-co-glycolide) samples of compositions ranging from (75:25) to (65:35) to (50% (65:35):50% (50:50)) were gamma-irradiated under ambient conditions in air. The irradiation doses used were 15, 20, 25, and 30 kGy. The generation of radicals resulting from the gamma-irradiation was confirmed using EPR. Two major radical species were observed and identified as centered at alkyl and alkyl peroxy groups. The indication from the X-band (9 GHz) frequencies showed that alkyl radicals gave rise to a quartet hyperfine pattern. However, measurements performed at higher W-band frequencies (90 GHz) showed that the X-band spectra are actually a composite profile arising from a series of overlapping individual resonances. Using combined EPR and ENDOR (Electron-Nuclear DOuble Resonance) measurements, an alkyl peroxy radical was identified. For increasing glycolide concentration from 75:25 to the 50:50 blend, there was a factor of 7 increase in the concentration of radicals A and B. Furthermore, both radical species were found to be stable for several weeks after storage at ambient temperature conditions. At elevated temperatures and humidities, radical stability decreased--the decay rate was estimated at approximately 3x10(-8) mol K(-1). The stability characteristics of the radicals under different conditions are attributed to changes in the morphology of the polymer.

Gamma Rays↗