Loss Of HF Research Articles

The formation of the granite complex in the Wuhe Mari area of Bayankala Mountain on the northeastern margin of the Tibetan Plateau: constraints from lithogeochemistry and U–Pb zircon dating

The granite complex in the Wuhe Mari area lies in the tectonic magma belt of the North Bayankala Mountains on the northeastern edge of the Qinghai-Tibet Plateau. It is located in the middle of the first member of the Changmahe Formation of the Early and Middle Triassic Bayankala Mountains Group. This article presents a systematic study of the petrological and geochemical characteristics and chronology of porphyrite granilite, monzogranite, porphyritic monzogranite and diorite in the granite complex in Wuhe Mari area. The genetic relationship between these four rock types as well as the type of source area and tectonic environment are clarified. Zircon LA-ICP-MS-U–Pb dating shows that the porphyritic granodiorite, monzogranite, porphyritic monzogranite and diorite have ages of 221.0 ± 2.7 Ma, 219.8 ± 3.0 Ma, 216.6 ± 4.3 Ma and 213.4 ± 1.6 Ma, respectively. The petrogeochemical characteristics show that the porphyritic granodiorite, monzogranite and porphyritic monzogranite in the granite complex have the characteristics of high Si, Al2O3, K, low Na, Ca, Mg, Fe, K, Rb and Th—Content in the strongly incompatible elements of the granite complex have three, the relative loss of Ba, Ta, Nb, Ce, slight enrichment or no anomaly, the loss of Sm, Hf and Zr, the strong loss of Y and Yb and the aluminum saturation index < 1.1. Combined with the geological data all three samples belong to Type I granite formed in the same collision environment. Based on the lithogeochemical characteristics and the results of U–Pb chronology, these three rock formations are believed to have been formed by a series of magmatic melting events and are the result of homologous magma crystallization and differentiation. The diorite forms in an intraplate tectonic setting as a result of the evolution of co-collision granite to intraplate granite.

In-Electrospray source Hydrogen/Deuterium exchange coupled to multistage fragmentation for the investigation of the protonation and fragmentation pathways of gas phase ions.

Identification of molecules in complex natural matrices relies on matching the fragmentation spectra of ions under investigation and the spectra acquired for the corresponding analytical standards. Currently, there are many databases of experimentally measured tandem mass spectrometry spectra (such as NIST, MzCloud, and Metlin), and considerable progress has been made in the development of software for predicting tandem mass spectrometry fragments in silico using combinatorial, machine learning, and quantum chemistry approaches (such as MetFrag, CFM-ID, and QCxMS). However, the electrospray ionization molecules can be ionized at different sites (protonated or deprotonated), and the fragmentation spectra of such ions are different. Here, we are using the combination of the in-ESI source hydrogen/deuterium exchange reaction and MSn fragmentation for the investigation of the fragmentation pathways for different protomers of organic molecules. It is shown that the distribution of the deuterium in the fragment ions reflects the presence of different protomers. For several molecules, the distribution of deuterium was traced up to the MS5 level of fragmentation revealing many unusual and unexpected effects. For example, we investigated the loss of HF from the ciprofloxacin and norfloxacin ions and observed that for ions protonated at -COOH group, the eliminating hydrogen always comes from -NH group. When ions are protonated at another site, the elimination of hydrogen with a probability of 30% occurs from the -NH group, and with a probability of 70%, it originates from other sites on the molecule. Such effects were not described previously. Quantum chemical simulation was used for the verification of the protonated structures and simulation of the corresponding fragmentation spectra.

Deciphering the irradiation induced fragmentation-rearrangement mechanisms in valence ionized CF3CH2F.

The increasing presence of 1,1,1,2-tetrafluoroethane (CF3CH2F) in the atmosphere has prompted detailed studies into its complex photodissociation behavior. Experiments focusing on CF3CH2F irradiation have unveiled an array of ions, with the persistent observation of the rearrangement product CHF2+ not yet fully understood. In this work, we combine density functional theory, coupled-cluster calculations with a complete basis set formalism, and atom-centered density matrix propagation molecular dynamics to investigate the energetics and dynamics of different potential pathways leading to CHF2+. We found that the two-body dissociation pathway involving an HF rearrangement, which was previously considered complex for CHF2+ formation, is actually straightforward but not likely due to the facile loss of HF. In contrast, our calculations reveal that the H elimination pathway, once thought of as a potential route to CHF2+, is not only comparably disadvantageous from both thermodynamic and kinetic points of view but also does not align with experimental data, particularly the lack of a rebound peak at m/z 101-102. We establish that the formation of CHF2+ is predominantly via the HF elimination channel, a conclusion experimentally corroborated by studies involving the trifluoroethylene cation CF2CHF+, a key intermediate in this process.

Fluorinated Propionic Acids Unmasked: Puzzling Fragmentation Phenomena of the Deprotonated Species.

Environmental contamination by per- and polyfluorinated substances (PFAS) is an emerging concern for the public. In this study, short-chain PFAS such as deprotonated per- and polyfluorinated propionic acids are investigated using a combination of infrared multiple-photon dissociation (IRMPD) spectroscopy, collision-induced dissociation (CID), and density functional theory calculations. IRMPD and CID proceed via multiple competing pathways: (1) production of fluoroformate (FCO2-) and the associated ethylene derivative, (2) production of HF and the associated carbanion, or (3) loss of CO2 and the associated carbanion. Fluorinated propionic acids with at least one fluorine atom bound to the terminal carbon yield FCO2-, whereas loss of HF is observed in polyfluorinated species with at least one fluorine atom bound to the α-carbon. To explore the reaction pathways of the various fluorinated propionic acids, the nudged elastic band method is employed. The relative energy of the four-membered ring transition state leading to FCO2- dictates which product channel is observed in dissociation.

Infrared laser ablation of poly(vinylidene fluoride): The Loss of HF

The mechanism and kinetics of infrared laser ablation of poly(vinylidene fluoride) (PVDF) in vacuum have been investigated to understand how this can be used as a polymer processing technology. The laser heats the surface and initiates decomposition of macromolecules in the molten polymer layer which rapidly leads to production of an ablative flow of polymer decomposition products. There is only a short induction period of up to 2 s before ablation begins. After the initial period, the rate of mass loss increases linearly with the time of laser exposure. Spherical particles with an average diameter of about 100 nm are formed on the surface of the powder coating obtained by laser ablation. The particle distribution ranges from 50 nm to 300 nm. The main gaseous product of ablation is HF from dehydrofluorination. A seccond important ablation process is the formation of gaseous carbenes generated during secondary reactions. Proposed ablation reactions due to laser-induced thermal dehydrofluorination occur in two stages. In the first stage, a double bond appears in PVDF due to direct loss of HF. Subsequent detachment of HF leads to the appearance of both triple bonds and cumulene bonds.

Thermal decomposition of perfluorinated carboxylic acids: Kinetic model and theoretical requirements for PFAS incineration

Thermal decomposition of high-fluorine content PFAS streams for the disposal of old generations of concentrates of firefighting foams, exhausted ion-exchanged resins and granular activated carbon, constitutes the preferred method for destruction of these materials. This contribution studies the thermal transformation of perfluoropentanoic acid (C4F9C(O)OH, PFPA), as a model PFAS species, in gas-phase reactions over broad ranges of temperature and residence time, which characterise incinerators and cement kilns. Our focus is only on gas-phase reactions, to formulate a gas-phase submodel that, in future, could be used in comprehensive simulation of thermal destruction of PFAS; such comprehensive models will need to comprise fluorine mineralisation on flyash and in clinker material. Our submodel consists of 56 reactions and 45 species, and includes new pathways that cover the initial decomposition channels of PFPA, including those that lead to the formation of the n-C4F9 radical, the abstraction of hydroxyl H by O/H radicals, the fragmentation of the n-C4F9 radical, reactions between HF and perfluoropentanoic acid, as well as between HF and heptafluorobutanoyl fluoride (C3F7COF), and the cyclisation reactions. The model illustrates the formation of a wide spectrum of small CnFm and CnHFm compounds in the temperature window of 800–1500 K, 2 and 25 s residence time in a plug flow reactor, providing theoretical estimates for the operating conditions of PFAS thermal destruction systems. The initiation reactions involve the loss of HF and formation of the transition α-lactone species that converts to C3F7COF, with C4F9C(O)OH completely decomposed at 1020 K for 2 s residence time. At 1500 K, we predict the emission of ꞉CF2 (biradical difluorocarbene), HF, CO2, CO, CF4, C2F6, and C2F4, but at < 1400 K, we note the formation of 1H-nonafluorobutane (C4HF9), phosgene (COF2), and heptafluorobutanoyl fluoride (C3F7COF), with 1-C4F8, 2-C4F8 and C3HF7 persisting to 1500 K. We demonstrate that, the gas-phase pyrolysis processes by themselves convert PFAS to HF and short-chain fluorocarbons, with similar product distribution for short (2 s) and long (25 s) residence times, as long as the treatment temperature exceeds 1500 K. These residence times reflect those encountered in incinerators and cement kilns, respectively. Thermokinetic and mechanistic insights revealed herein shall assist to innovate PFAS thermal disposal technologies, and, from a fundamental perspective, to accelerate research progress in modelling of gas/solid reactions that mineralise PFAS-derived fluorine.

Regioselective formation of fluorinated metallacycles from fluoroalkenes and an electron-rich Ni(0) difluorocarbene

The reactivity of an electron-rich Ni-difluorocarbene complex, Ni=CF2(dppe)[P(OMe)3] (1), with a variety of fluorinated alkenes was investigated (dppe = 1,2-bis(diphenylphosphino)ethane). Reactions of 1 with perfluoro(methyl vinyl ether) and chlorotrifluoroethylene (CTFE) give regiospecific formation of metallacyclobutanes, in which the carbene C attacks the most electron-rich carbon of the fluoroalkene. Further reaction of the CTFE-derived metallacycle in the presence of tetrahydrofuran affords a single isomer of NiCl(σ-CF2CF=CFH) (dppe), 8, proposed to be formed by Ni-mediated Cα-Cl activation followed by hydride abstraction and loss of HF. Although 1 also undergoes a cyclization reaction with trifluoroethylene (TrFE), instability of the presumed nickelacyclobutane affords the C3 fluoroalkene, F2C=CH(CF3), and subsequent formation of isomeric metallacyclopentanes from two additional TrFEs. Alternatively, reaction of 1 with hexafluoropropene forms an unexpected Ni–CF3 σ-perfluoroallyl complex.

Synthesis and thermal stability of rare earth compounds REF3, REF3·nH2O and (H3O)RE3F10·nH2O (RE = Tb − Lu, Y), obtained from sulphide precursors

The nature of the interaction between sulphides of the rare-earth elements (RE) of the yttrium subgroup RE2S3 (Dy − Lu, Y) with hydrofluoric acid (concentration of 49%) was studied. Powders of RE2S3 compounds were obtained by the reaction between RE2O3 (Dy − Lu, Y) and Tb4O7 with a stream of H2S and CS2 in the 1000–1050 °C temperature range. The reaction between RE2S3 and HF was carried out in a glassy carbon crucible in the 21–25 °C temperature range in solution, and the precipitate was washed with H2O and dried at 90–100 °C. For the hydrates of RE fluorides with decreasing RE radius, the RE content increases the sorption of water for TbF3·0.5H2O; DyF3·0.5H2O; YF3·0.5H2O; HoF3·0.8H2O; and ErF3·0.9H2O. The powders of REF3·nH2O consisted of micro- and nano-sized particles containing the amorphous phase. Water loss occurs in the 50–180 °C temperature range and is accompanied by a natural increase in enthalpy: from 23.6 J/g for TbF3 · 0.5H2O to 97.8 J/g for ErF3·0.9H2O and from 51.1 J/g for (H3O)Tm3F10·1.7H2O to 64.5 J/g for (H3O)Lu3F10·0.9H2O. Exothermic effects of formation of polycrystalline phase REF3 were recorded in the 200–300 °C temperature range. The reaction of RE2S3 (Tm, Yb, Lu) powders with HF proceeds with the formation of the zeolite type compounds (H3O)Tm3F10·1.7H2O, (H3O)Yb3F10·1.0H2O and (H3O)Lu3F10·0.9H2O. Thermal dissociation occurs with gradual loss of water and HF to form RE fluorides with the β-YF3 structure as described by

Low energy electron induced reactions in fluorinated acetamide – probing negative ions and neutral stable counterparts*

Electron impact to trifluoroacetamide (CF3CONH2, TFAA) in the energy range 0–12 eV leads to a variety of negative fragment ions which are formed via dissociative electron attachment (DEA). The underlying reactions range from single bond cleavages to remarkably complex reactions that lead to loss of the neutral units HF, H2O and HNCO as deduced from their directly observed ionic counterparts (M – H2O)−, (M – HF)− and (M – HNCO)−. Also formed are the pseudo-halogen ions CN− and OCN−. All these reactions proceed dominantly via a resonance located near 1 eV, i.e., electrons at subexcitation energies trigger reactions involving multiple bond cleavages. The electron induced generation of the neutral molecules HF, H2O and HNCO in condensed TFAA films is probed by temperature controlled thermal desorption spectrometry (TDS) which can be viewed as a complementary techniques to gas-phase experiments in DEA to directly probe the neutral counterparts.

Selective Activation of Fluoroalkenes with N‐Heterocyclic Carbenes: Synthesis of N‐Heterocyclic Fluoroalkenes and Polyfluoroalkenyl Imidazolium Salts

Selective reactions between nucleophilic N,N'-diaryl-heterocyclic carbenes (NHCs) and electrophilic fluorinated alkenes afford NHC fluoroalkenes in high yields. These stable compounds undergo efficient and selective fluoride abstraction with Lewis acids to give polyfluoroalkenyl imidazolium salts. These salts react at Cβ with pyrrolidine to give ammonium fluoride-substituted salts, which give rise to conjugated imidazolium-enamine salts through loss of HF. Alternatively, reaction with 4-(dimethylamino)-pyridine provides a Cα-pyridinium-substituted NHC fluoroalkene. These compounds were studied using multinuclear NMR spectroscopy, mass spectrometry, and X-ray crystallography. Insight into their electronic structure and reactivity was gained through the use of DFT calculations.

Identification of Novel Metabolic Pathways of Sitagliptin (STG) by LC/MS and LC/MS2 after Incubations with Rat Hepatocytes

Sitagliptin (STG), a drug for treating Type Ii Diabetes Mellitus (T2DM), has been associated with severe joint pain in some patients. In this paper the metabolic profile of the drug has been investigated in order to determine metabolism and formation of reactive compounds which may contribute to this adverse effect. Metabolism of STG was investigated in vitro by incubation with freshly isolated Sprague-Dawley rat hepatocytes, to characterize Phase I and II metabolites, and the reaction mixture analysed on a zwitter ionic hydrophilic interaction (ZIC®-HILIC) column using LC-MS and LC-MS2 utilising electrospray ionization (ESI) in the positive ion mode. STG was metabolised to yield eleven metabolites, but in total only 3.1% of the parent drug was metabolised over 2 hrs incubation. These metabolites were structurally characterized on the basis of accurate mass analyses and the major metabolic routes for STG determined to be via aromatic oxidation (0.86%) and desaturation of N-C and C-C of the piperazine (0.44%). Novel metabolites of STG detected using these methods included STG N-glucuronide (M6) and a di-ketone metabolite (M4), hydroxylation of both the amine group and aromatic ring followed by formation of glucuronide metabolites (M5, M5’), oxidative desaturation of NH2 and di-hydroxylation of metabolites followed by loss of HF. Also, observed was an N-sulfate metabolite (0.07%) and acetylation followed by glucuronide conjugation was also found in trace amounts (<0.01%). MS2 fragment ions provide additional structural confirmation providing a possible structure for most metabolites such as by fragment ion loss of the glucuronide group (176 Da) from metabolite M5 and loss of the phenolic sulfate (80 Da) of N-Sulfate metabolite (M7). Reduction reaction of piperazine ring probably generates highly electrophilic metabolite of STG, which may be susceptible to produce adverse effects. Furthermore, N-oxidation reaction forming reactive intermediates metabolic to give a hydroxylamine metabolite that may undergo further reactions to yield electrophilic intermediate metabolites.

One-electron oxidation of gemcitabine and analogs: mechanism of formation of C3' and C2' sugar radicals.

Gemcitabine is a modified cytidine analog having two fluorine atoms at the 2′-position of the ribose ring. It has been proposed that gemcitabine inhibits RNR activity by producing a C3′• intermediate via direct H3′-atom abstraction followed by loss of HF to yield a C2′• with 3′-keto moiety. Direct detection of C3′• and C2′• during RNR inactivation by gemcitabine still remains elusive. To test the influence of 2′- substitution on radical site formation, electron spin resonance (ESR) studies are carried out on one-electron oxidized gemcitabine and other 2′-modified analogs, i.e., 2′-deoxy-2′-fluoro-2′-C-methylcytidine (MeFdC) and 2′-fluoro-2′-deoxycytidine (2′-FdC). ESR line components from two anisotropic β-2′-F-atom hyperfine couplings identify the C3′• formation in one-electron oxidized gemcitabine, but no further reaction to C2′• is found. One-electron oxidized 2′-FdC is unreactive toward C3′• or C2′• formation. In one-electron oxidized MeFdC, ESR studies show C2′• production presumably from a very unstable C3′• precursor. The experimentally observed hyperfine couplings for C2′• and C3′• match well with the theoretically predicted ones. C3′• to C2′• conversion in one-electron oxidized gemcitabine and MeFdC has theoretically been modeled by first considering the C3′• and H3O+ formation via H3′-proton deprotonation and the subsequent C2′• formation via HF loss induced by this proximate H3O+. Theoretical calculations show that in gemcitabine, C3′• to C2′• conversion in the presence of a proximate H3O+ has a barrier in agreement with the experimentally observed lack of C3′• to C2′• conversion. In contrast, in MeFdC, the loss of HF from C3′• in the presence of a proximate H3O+ is barrierless resulting in C2′• formation which agrees with the experimentally observed rapid C2′• formation.

Fragmentation of Moxifloxacin and Its Analogs by Electrospray Ionization Time-of-Flight Mass Spectrometry

The fragmentation of patterns of moxifloxacin, 2-N-methylated moxifloxacin (analog 1), and 1-cyclopropyl-6,7-difluoro-8-methoxy-4-oxo-3-quinolinecarboxylic acid (analog 2) were investigated by electrospray ionization quadrupole time-of-flight tandem mass spectrometry in the positive-ion mode. Many unusual ions were detected in the tandem mass spectra of moxifloxacin. Although the structures of moxifloxacin and analog 1 were similar, the relative abundances of products varied greatly. Comparison of the relative abundances of the product ions that lost CO2 or H2O and complementary product ions resulting from sequential four-membered hydrogen rearrangement showed that the differences were related to the protonation sites. The loss of HF, probably though the formation of an ion/neutral complex, is of scientific interest. The identities of the major product ions were confirmed by deuterium-labeling experiments that demonstrated an unusual loss of a deuterium atom. The major differences in fragmentation patterns were compared to previous reports in the literature.

Extreme Space Weather Impact: An Emergency Management Perspective

AbstractIn 2010, the Department of Homeland Security's Federal Emergency Management Agency (FEMA) partnered with the National Oceanic and Atmospheric Administration's Space Weather Prediction Center (SWPC) to investigate the potential for extreme space weather conditions to impact National Security/Emergency Preparedness communications—those communications vital to a functioning government and to emergency and disaster response—in the United States. Given the interdependencies of modern critical infrastructure, the initial systematic review of academic research on space weather effects on communications expanded to other critical infrastructure sectors, federal agencies, and private sector organizations. While the effort is ongoing, and despite uncertainties inherent with this hazard, FEMA and the SWPC did draw some conclusions. If electric power remains available, an extreme space weather event will result in the intermittent loss of HF and similar sky wave radio systems, minimal direct impact to public safety line‐of‐sight radio and commercial cellular services, a relatively small loss of satellite services as a percentage of the total satellite fleet, interference or intermittent loss of satellite communications and GPS navigation and timing signals, and no first‐order impact to consumer electronic devices. Vulnerability of electric power to an extreme geomagnetic storm remains the primary concern from an emergency management perspective, but actual impact is not well understood at present. A discussion of potential impacts to infrastructure from the loss of electric power from any hazard is provided using the 2011 record tornado outbreak in Alabama as an example.

Formation and Fragmentation of Unsaturated Fatty Acid [M – 2H + Na]– Ions: Stabilized Carbanions for Charge-Directed Fragmentation

Fatty acids are long-chain carboxylic acids that readily produce [M - H](-) ions upon negative ion electrospray ionization (ESI) and cationic complexes with alkali, alkaline earth, and transition metals in positive ion ESI. In contrast, only one anionic monomeric fatty acid-metal ion complex has been reported in the literature, namely [M - 2H + Fe(II)Cl](-). In this manuscript, we present two methods to form anionic unsaturated fatty acid-sodium ion complexes (i.e., [M - 2H + Na](-)). We find that these ions may be generated efficiently by two distinct methods: (1) negative ion ESI of a methanolic solution containing the fatty acid and sodium fluoride forming an [M - H + NaF](-) ion. Subsequent collision-induced dissociation (CID) results in the desired [M - 2H + Na](-) ion via the neutral loss of HF. (2) Direct formation of the [M - 2H + Na](-) ion by negative ion ESI of a methanolic solution containing the fatty acid and sodium hydroxide or bicarbonate. In addition to deprotonation of the carboxylic acid moiety, formation of [M - 2H + Na](-) ions requires the removal of a proton from the fatty acid acyl chain. We propose that this deprotonation occurs at the bis-allylic position(s) of polyunsaturated fatty acids resulting in the formation of a resonance-stabilized carbanion. This proposal is supported by ab initio calculations, which reveal that removal of a proton from the bis-allylic position, followed by neutral loss of HX (where X = F(-) and (-)OH), is the lowest energy dissociation pathway.

Dissociative electron attachment to hexafluoroacetylacetone and its bidentate metal complexes M(hfac)2; M = Cu, Pd

Beta-diketones are a versatile class of compounds that can complex almost any metal in the periodic table of elements. Their metal complexes are found to be fairly stable and generally have sufficient vapor pressure for deposition techniques requiring volatile metal sources. Motivated by the potential role of low energy electrons in focused electron beam induced deposition, we have carried out a crossed electron∕molecular beam study on the dissociative electron attachment and non-dissociative electron attachment (NDEA) to hexafluoroacetylacetone (HFAc) and its bidentate metal complexes: bis-hexafluoroacetylacetonate copper(II), Cu(hfac)2 and bis-hexafluoroacetylacetonate palladium(II), Pd(hfac)2. The relative ion yield curves for the native precursor to the ligand as well as its stable, 16 valence electron Pd(II) complex and open shell, 17 valence electron Cu(II) complex, are presented and compared. For HFAc, the loss of HF leads to the dominant anion observed, and while NDEA is only weakly pronounced for Pd(hfac)2 and loss of hfac(-) is the main dissociation channel, [Cu(hfac)2](-) formation from Cu(hfac)2 dominates. A comparison of the ion yield curves and the associated resonances gives insight into the role of the ligand in the attachment process and highlights the influence of the central metal atom.

Molecular rearrangement reactions in the gas phase triggered by electron attachment

Bond formation and rearrangement reactions in gas phase electron attachment were studied through dissociative electron attachment (DEA) to pentafluorotoluene (PFT), pentafluoroaniline (PFA) and pentafluorophenol (PFP) in the energy range 0-14 eV. In the case of PFA and PFP, the dominant processes involve formation of [M - HF](-) through the loss of neutral HF. This fragmentation channel is most efficient at low incident electron energy and for PFP it is accompanied by a substantial conformational change of the anionic fragment. At higher energy, HF loss is also observed as well as a number of other fragmentation processes. Thermochemical threshold energies have been computed for all the observed fragments and classical trajectories of the electron attachment process were calculated to elucidate the fragmentation mechanisms. For the dominant reaction channel leading to the loss of HF from PFP, the minimum energy path was calculated using the nudged elastic band method.

Fluoronium metathesis and rearrangements of fluorine-stabilized carbocations

The ion–molecule reaction of gaseous trifluoromethyl cation with the conjugated enone 3-methylcyclopentenone yields the C 6H 8F + product from metathesis of F + with the ketone oxygen, along with concomitant formation of neutral carbonyl fluoride. Comparison of the infrared multiple photon dissociation (IRMPD) spectrum of the product ion with that predicted by anharmonic DFT shows a good match. The IRMPD action spectrum, monitored by expulsion of hydrogen fluoride to form C 6H 7 + ( m/z 79), shows that the ion–molecule reactions of CF 3 + with two other isomeric, conjugated enones, cyclohexenone and 2-methylcyclopentenone, also yield the same product ion as results from 3-methylcyclopentenone. Although CF 3 + is a comparatively soft Lewis acid (by comparison to the isoelectronic BF 3), formation of the most stable C 6H 8F + isomer (the one observed experimentally) cannot be accounted for by attachment of CF 3 + to the C C bond of a neutral enone. IRMPD of the C 6H 7 + ion formed by reaction of CF 3 + with 2-methylcyclopentenone, monitored by loss of H 2, indicates that the C 6H 7 + ion consists of a mixture of protonated benzene and protonated fulvene. Neither of those C 6H 7 + ions can be produced by unimolecular loss of HF from C 6H 8F + without prior rearrangement. Plausible pathways for reversible skeletal isomerization of C 6H 8F +, probed by DFT, suggest the intervention of nonclassical, edge-protonated cyclopropane transition states, analogous to the rearrangement of the cyclohexyl cation to the 1-methylcyclopentyl cation.

Implications of garnet resorption for the Lu-Hf garnet geochronometer: an example from the contact aureole of the Makhavinekh Lake Pluton, Labrador

In the contact aureole of the Makhavinekh Lake Pluton (MLP), Labrador, garnet resorption caused redistribution of Lu and loss of Hf, creating spuriously young Lu-Hf garnet ages. Garnet grew during granulite facies regional metamorphism at 1860-1850 Ma. At 1322 Ma, garnet rims were replaced by coronas of cordierite and orthopyroxene during contact metamorphism. Garnet-ilmenite Lu-Hf geochronology using bulk-garnet separates yields apparent ages that young from 1876 ± 21 Ma at 4025 m from the contact to 1396 ± 8 Ma at 450 m from the contact. Toward the contact, garnet crystals are progressively more resorbed. Concentrations of Lu measured by LA-ICP-MS along radial traverses on central sections through relict garnet decrease gently away from the cores but rise steeply within 50-200 lm of the edges of the relicts. Enrichments of Lu in rims of relict garnet demonstrates strong partitioning of Lu into garnet during resorption and modest intracrystalline diffusion. Hafnium distributions could not be measured, but considering the strong incompatibility of Hf with garnet, it is likely that nearly all Hf in resorbed portions of the garnet was lost from the crystals. Lu-Hf ages in the aureole are thus controlled predominantly by this retention of Lu and loss of Hf during garnet resorption. This deduction was tested with a simple numerical model in which the partial retention of Lu and loss of Hf is tracked as a population of garnet is resorbed. Assuming a spherical geometry for garnet porphyroblasts, Rayleigh fractionation is used to approximate initial Lu zoning profiles ranging from flat to steeply decreasing toward garnet rims. The model simulates: (i) Lu-Hf decay for a specified period before resorption; (ii) instantaneous resorption with retention of Lu and loss of Hf from the resorbed portion of the crystal and (iii) Lu-Hf decay during a specified period after resorption. Several parameters influence the modelled age, but garnet resorption and Lu retention are the primary factors. When all other parameters are held constant, larger amounts of resorption and higher degrees of Lu retention produce younger apparent ages (false ages). Similarly, flatter initial Lu profiles yield younger apparent ages as a consequence of the larger proportion of Lu and Hf that resides in the outer portions of the porphyroblast. The difference between the apparent and actual ages is greater if the duration of the pre-resorption decay period is large relative to the post-resorption decay period. Larger crystals in a Gaussian crystal-size distribution (CSD) generally dominate the Lu-Hf budget and produce an older apparent age relative to the age of the mean crystal size. Compared to a symmetrical Gaussian CSD, positively skewed CSDs result in reduced resorption of large crystals and produce an older apparent age. Application of the model to the MLP aureole, positing growth at 1850 Ma and resorption at 1320 Ma, yields model ages that young from 1850 to 1374 Ma toward the contact, in good agreement with the apparent ages determined from geochronology.

1,5‐electrocyclization versus 1,5‐proton shift in imidazolium allylides and 2‐phospha‐allylides: a DFT investigation

The competitive 1,5‐electrocyclization versus intramolecular 1,5‐proton shift in imidazolium allylides and imidazolium 2‐phosphaallylides has been investigated theoretically at the DFT (B3LYP/6‐311 + +G**//B3LYP/6‐31G**) level. 1,5‐Electrocyclization follows pericyclic mechanism and its activation barrier is lower than that for the pseudopericyclic mechanism by ∼5–6 kcal mol−1. The activation barriers for 1,5‐electrocyclization of imidazolium 2‐phosphaallylides are found to be smaller than those for their nonphosphorus analogues by ∼3–5 kcal mol−1. There appears to be a good correlation between the activation barrier for intramolecular 1,5‐proton shift and the density of the negative charge at C8, except for the ylides having fluorine substituent at this position (7b and 8b). The presence of fluorine atom reduces the density of the negative charge at C8 (in 7b it becomes positively charged) and thus raises the activation barrier. The ylides 7f and 8f having CF3 group at C8, in preference to the 1,5‐proton shift, follow an alternative route leading to different carbenes which is accompanied by the loss of HF. The carbenes Pr7,8b–e resulting from intramolecular 1,5‐proton shift have a strong tendency to undergo intramolecular SN2 type reaction, the activation barrier being 7–28 kcal mol−1. Copyright © 2011 John Wiley &amp; Sons, Ltd.