Biodiversity of Parasitic Hymenoptera Across Sky Islands of Arkansas, United States.

Sky islands are often areas of endemism and high species diversity around the world. In central North America, the Ozark and Ouachita Highlands contain numerous modestly high elevational islands that are slightly cooler and wetter than surrounding lowlands and these areas are known to contain many unique species. We studied parasitic Hymenoptera biodiversity on three sky islands in Arkansas, both in canopy and understory strata of mature post oak forests. We found that morphospecies diversity was high, and community structure varied both within (canopy versus understory) and between sky islands. Each mountaintop showed a high level of distinctiveness with few morphospecies found in multiple locations. The high intersky island variation indicates that individual sky islands in the region harbor unique Hymenoptera assemblages, a pattern that likely extends to the broader insect community. Our study suggests that these highland areas are important regions of North American biodiversity and that they should be evaluated individually for conservation efforts in order to preserve their distinctive community structure.

Opposing global change drivers counterbalance trends in breeding North American monarch butterflies.

Many insects are in clear decline, with monarch butterflies (Danaus plexippus) drawing particular attention as a flagship species. It is well documented that, among migratory populations, numbers of overwintering monarchs have been falling across several decades, but trends among breeding monarchs are less clear. Here, we compile >135,000 monarch observations between 1993 and 2018 from the North American Butterfly Association's annual butterfly count to examine spatiotemporal patterns and potential drivers of adult monarch relative abundance trends across the entire breeding range in eastern and western North America. While the data revealed declines at some sites, particularly the US Northeast and parts of the Midwest, numbers in other areas, notably the US Southeast and Northwest, were unchanged or increasing, yielding a slightly positive overall trend across the species range. Negative impacts of agricultural glyphosate use appeared to be counterbalanced by positive effects of annual temperature, particularly in the US Midwest. Overall, our results suggest that population growth in summer is compensating for losses during the winter and that changing environmental variables have offsetting effects on mortality and/or reproduction. We suggest that density-dependent reproductive compensation when lower numbers arrive each spring is currently able to maintain relatively stable breeding monarch numbers. However, we caution against complacency since accelerating climate change may bring growing threats. In addition, increases of summer monarchs in some regions, especially in California and in the south, may reflect replacement of migratory with resident populations. Nonetheless, it is perhaps reassuring that ubiquitous downward trends in summer monarch abundance are not evident.

Complex life histories predispose aphids to recent abundance declines.

Many animals change feeding habits as they progress through life stages, exploiting resources that vary in space and time. However, complex life histories may bring new risks if rapid environmental change disrupts the timing of these switches. Here, we use abundance times series for a diverse group of herbivorous insects, aphids, to search for trait and environmental characteristics associated with declines. Our meta dataset spanned three world regions and >300 aphid species, tracked at 75 individual sites for 10-50 years. Abundances were generally falling, with median changes of -8.3%, -5.6%, and -0.1% per year in the central USA, northwestern USA, and United Kingdom, respectively. Aphids that obligately alternated between host plants annually and those that were agricultural pests exhibited the steepest declines, relative to species able to persist on the same host plant year-round or those in natural areas. This suggests that host alternation might expose aphids to climate-induced phenology mismatches with one or more of their host plant species, with additional risks from exposure to insecticides and other management efforts. Warming temperatures through time were associated with milder aphid declines or even abundance increases, particularly at higher latitudes. Altogether, while a warming world appeared to benefit some aphid species in some places, most aphid species that had time-sensitive movements among multiple host plants seemed to face greater risk of decline. More generally, this suggests that recent human-induced rapid environmental change is rebalancing the risks and rewards associated with complex life histories.

Recent climate change is creating hotspots of butterfly increase and decline across North America.

Some insect populations are experiencing dramatic declines, endangering the crucial ecosystem services they provide. Yet, other populations appear robust, highlighting the need to better define patterns and underlying drivers of recent change in insect numbers. We examined abundance and biodiversity trends for North American butterflies using a unique citizen-science dataset that has recorded observations of over 8 million butterflies across 456 species, 503 sites, nine ecoregions, and 26 years. Butterflies are a biodiverse group of pollinators, herbivores, and prey, making them useful bellwethers of environmental change. We found great heterogeneity in butterfly species' abundance trends, aggregating near zero, but with a tendency toward decline. There was strong spatial clustering, however, into regions of increase, decrease, or relative stasis. Recent precipitation and temperature appeared to largely drive these patterns, with butterflies generally declining at increasingly dry and hot sites but increasing at relatively wet or cool sites. In contrast, landscape and butterfly trait predictors had little influence, though abundance trends were slightly more positive around urban areas. Consistent with varying responses by different species, no overall directional change in butterfly species richness or evenness was detected. Overall, a mosaic of butterfly decay and rebound hotspots appeared to largely reflect geographic variability in climate drivers. Ongoing controversy about insect declines might dissipate with a shift in focus to the causes of heterogeneous responses among taxa and sites, with climate change emerging as a key suspect when pollinator communities are broadly impacted.

No net insect abundance and diversity declines across US Long Term Ecological Research sites.

Recent reports of dramatic declines in insect abundance suggest grave consequences for global ecosystems and human society. Most evidence comes from Europe, however, leaving uncertainty about insect population trends worldwide. We used >5,300 time series for insects and other arthropods, collected over 4-36 years at monitoring sites representing 68 different natural and managed areas, to search for evidence of declines across the United States. Some taxa and sites showed decreases in abundance and diversity while others increased or were unchanged, yielding net abundance and biodiversity trends generally indistinguishable from zero. This lack of overall increase or decline was consistent across arthropod feeding groups and was similar for heavily disturbed versus relatively natural sites. The apparent robustness of US arthropod populations is reassuring. Yet, this result does not diminish the need for continued monitoring and could mask subtler changes in species composition that nonetheless endanger insect-provided ecosystem services.

Potential for Reclamation of Abandoned Gas Wells to Restore Ecosystem Services in the Fayetteville Shale of Arkansas.

Unconventional oil and gas (UOG) drilling has expanded rapidly across the United States, including in the Fayetteville Shale formation in north-central Arkansas where drilling began in 2004. As one of the oldest regions of UOG activity in the United States, this area has experienced significant land-use changes, specifically development of natural habitat and agricultural land for gas infrastructure. In recent years, drilling of new wells has stopped and production has declined. By 2017, 1038 wells had ceased production and been abandoned, which makes them eligible for land reclamation. However, most of these sites (80%) have not been reclaimed and continue to cause losses in ecosystem services. If reclamation was performed on lands associated with abandoned infrastructure, we estimate more than $2 million USD annually in agricultural, timber, and carbon sequestration values would be gained. These benefits far outweigh the costs of reclamation, especially since the benefits accrue over time and reclamation is a short-term cost. Our estimates indicate a 2-4 year break-even time period when cumulative ecosystem services benefits will outweigh reclamation costs. We predicted a well-abandonment rate of 155 per year until 2050 when 98% of wells will be abandoned, which indicates great potential for future ecosystem services restoration. Thus, we recommend that Arkansans at the government and citizen level work to restore lands impacted by UOG development in the Fayetteville Shale region so that their value to landowners and society can be recovered, which will enhance long-term economic and environmental benefits.

Cut points of the Actigraph GT9X for moderate and vigorous intensity physical activity at four different wear locations.

Accelerometer cut points are an important consideration for distinguishing the intensity of activity into categories such as moderate and vigorous. It is well-established in the literature that these cut points depend on a variety of factors, including age group, device, and wear location. The Actigraph GT9X is a newer model accelerometer that is used for physical activity research, but existing cut points for this device are limited since it is a newer device. Furthermore, there is not existing data on cut points for the GT9X at the ankle or foot locations, which offers some potential benefit for activities that do not involve arm and/or core motion. A total of N = 44 adults completed a four-stage treadmill protocol while wearing Actigraph GT9X sensors at four different locations: foot, ankle, wrist, and hip. Metabolic Equivalent of Task (MET) levels assessed by indirect calorimetry along with Receiver Operating Characteristic (ROC) curves were used to establish cut points for moderate and vigorous intensity for each wear location of the GT9X. Area under the ROC curves indicated high discrimination accuracy for each case.

A Comparison of the Impacts of Wind Energy and Unconventional Gas Development on Land-use and Ecosystem Services: An Example from the Anadarko Basin of Oklahoma, USA.

The United States energy industry is transforming with the rapid development of alternative energy sources and technological advancements in fossil fuels. Two major changes include the growth of wind turbines and unconventional oil and gas. We measured land-use impacts and associated ecosystem services costs of unconventional gas and wind energy development within the Anadarko Basin of the Oklahoma Woodford Shale, an area that has experienced large increases in both energy sectors. Unconventional gas wells developed three times as much land compared to wind turbines (on a per unit basis), resulting in higher ecosystem services costs for gas. Gas wells had higher impacts on intensive agricultural lands (i.e., row crops) compared to wind turbines that had higher impacts on natural grasslands/pastures. Because wind turbines produced on average less energy compared to gas wells, the average land-use-related ecosystem cost per gigajoule of energy produced was almost the same. Our results demonstrate that both unconventional gas and wind energy have substantial impacts on land use, which likely affect wildlife populations and land-use-related ecosystem services. Although wind energy does not have the associated greenhouse gas emissions, we suggest that the direct impacts on ecosystems in terms of land use are similar to unconventional fossil fuels. Considering the expected rapid global expansion of these two forms of energy production, many ecosystems are likely to be at risk.

Habitat Modification by the Leaf-Cutter Ant, Atta cephalotes, and Patterns of Leaf-Litter Arthropod Communities.

Ecosystem engineers are profoundly important in many biological communities. A Neotropical taxonomic group considered to have engineering effects is the Formicidae (ants). Leaf-cutter ants (LCAs), in particular, which form extensive colonies of millions of individuals, can be important ecosystem engineers in these environments. While the effects of LCAs on plant community structure and soil chemistry are well-studied, their effects on consumers are poorly understood. Therefore, we examined the indirect effects of the LCA Atta cephalotes L. on the leaf-litter arthropod community. We compared abundance and diversity patterns at ant nests to areas distant from nests, utilizing both a factorial design and gradient analysis for both nocturnal and diurnal arthropods. We found that arthropod abundance and diversity was significantly lower for multiple taxonomic groups and trophic levels near leaf-cutter nests, and this pattern was strongest at night. Exceptions to this pattern included two morphospecies of Collembola that were more abundant on nests, suggesting some specialization for these species. For the gradient analysis, abundance increased exponentially for most groups of arthropods. However, for the dominant arthropod species, the amphipod Cerrorchestia hyloraina Lindeman, a quadratic function was the best fit curvilinear model for abundance. It appeared that C. hyloraina had maximal abundance at the transition between nest site and less disturbed forest. These results indicate that LCA activity has a strong effect on the leaf-litter arthropod community, adding to spatial heterogeneity within neotropical forests. These effects may translate into changes in important ecological processes such as nutrient cycling and food web function.

Seed dispersal of Diospyros virginiana in the past and the present: Evidence for a generalist evolutionary strategy.

Several North American trees are hypothesized to have lost their co-evolved seed disperser during the late-Pleistocene extinction and are therefore considered anachronistic. We tested this hypothesis for the American persimmon (Diospyros virginiana) by studying the effects of gut passage of proposed seed dispersers on seedling survival and growth, natural fruiting characteristics, and modern animal consumption patterns. We tested gut passage effects on persimmon seeds using three native living species, the raccoon (Procyon lotor), Virginia opossum (Didelphis virginiana), and coyote (Canis latrans), and two Pleistocene analogs; the Asian elephant (Elephas maximus) and alpaca (Vicugna pacos). Persimmon seeds excreted by raccoons, coyotes, and elephants survived gut transit. Gut passage did not affect sprouting success, but did tend to decrease time to sprout and increase seedling quality. Under field conditions, persimmon fruits were palatable on the parent tree and on the ground for an equal duration, but most fruits were consumed on the ground. Seven vertebrate species fed upon persimmon fruits, with the white-tailed deer (Odocoileus virginianus)-a species not capable of dispersing persimmon seeds-comprising over 90% of detections. Conversely, potential living seed dispersers were rarely detected. Our results suggest the American persimmon evolved to attract a variety of seed dispersers and thus is not anachronistic. However, human-induced changes in mammal communities could be affecting successful seed dispersal. We argue that changes in the relative abundance of mammals during the Anthropocene may be modifying seed dispersal patterns, leading to potential changes in forest community composition.

Habitat loss and modification due to gas development in the Fayetteville shale.

Hydraulic fracturing and horizontal drilling have become major methods to extract new oil and gas deposits, many of which exist in shale formations in the temperate deciduous biome of the eastern United States. While these technologies have increased natural gas production to new highs, they can have substantial environmental effects. We measured the changes in land use within the maturing Fayetteville Shale gas development region in Arkansas between 2001/2002 and 2012. Our goal was to estimate the land use impact of these new technologies in natural gas drilling and predict future consequences for habitat loss and fragmentation. Loss of natural forest in the gas field was significantly higher compared to areas outside the gas field. The creation of edge habitat, roads, and developed areas was also greater in the gas field. The Fayetteville Shale gas field fully developed about 2% of the natural habitat within the region and increased edge habitat by 1,067 linear km. Our data indicate that without shale gas activities, forest cover would have increased slightly and edge habitat would have decreased slightly, similar to patterns seen recently in many areas of the southern U.S. On average, individual gas wells fully developed about 2.5 ha of land and modified an additional 0.5 ha of natural forest. Considering the large number of wells drilled in other parts of the eastern U.S. and projections for new wells in the future, shale gas development will likely have substantial negative effects on forested habitats and the organisms that depend upon them.

Bison grazing increases arthropod abundance and diversity in a tallgrass prairie.

How grazing-induced ecosystem changes by ungulates indirectly affect other consumers is a question of great interest. I investigated the effect of grazing by American Bison (Bos bison L.) on an arthropod community in tallgrass prairie. Grazing increased the abundance of arthropods, an increase that was present in both herbivorous and carnivorous assemblages, but not in detritivores. The increase in herbivores and reduction in plant biomass from grazing resulted in an arthropod herbivore load almost three times higher in grazed plots compared with controls. Among herbivores, the sap-feeding insect guild was dramatically more abundant, while chewing herbivores were not affected. Herbivorous and carnivorous arthropod richness was higher in grazed plots, although the response was strongest among herbivores. Arthropod abundance on individual grasses and forbs was significantly higher in grazed areas, while plant type had no effect on abundance, indicating that the change was ecosystem-wide and not simply in response to a reduction in grass biomass from grazing. The response of arthropods to grazing was strongest in the early part of the growing season. Published research shows that ungulate grazing, although decreasing available biomass to other consumers, enhances plant quality by increasing nitrogen level in plants. The arthropod results of this study suggest higher plant quality outweighs the potential negative competitive effects of plant biomass removal, although other activities of bison could not be ruled out as the causative mechanism. Because arthropods are extremely abundant organisms in grasslands and a food source for other consumers, bison may represent valuable management tools for maintaining biodiversity.

Positron-emission tomography imaging of the TSPO with [(18)F]FEPPA in a preclinical breast cancer model.

The present study aims to image the 18-kDa translocator protein (TSPO; formerly known as the peripheral benzodiazepine receptor) in a preclinical human breast cancer (BC) xenograft mouse model with positron-emission tomography (PET). An automated radiosynthesis of [(18)F]-N-(2-(2-fluoroethoxy)benzyl)-N-(4-phenoxypyridin-3-yl)acetamide ([(18)F]FEPPA) was validated for human use using a commercial synthesis module and resulted in a high radiochemical yield (30%±8%, uncorrected; n=54) and specific activity (6±4 Ci/µmol). Tumor uptake of [(18)F]FEPPA in mice bearing subcutaneous MDA-MB-231 BC xenografts was evaluated by PET-computed tomography imaging and ex vivo biodistribution studies. Although the tumor was successfully visualized, ex vivo biodistribution studies revealed low tumor uptake (0.7%ID/g), with the majority of radioactivity distributed in the spleen, muscle, and heart despite high TSPO expression in this cell line. Our laboratory routinely prepares [(18)F]FEPPA for human-imaging studies in the central nervous system, and we envision that radiopharmaceuticals that target the TSPO have the potential for imaging macrophages in the tumor microenvironment.

Development of new carbon-11 labelled radiotracers for imaging GABAA- and GABAB-benzodiazepine receptors.

Two quinolines identified as positive allosteric modulators of γ-aminobutyric acid (GABA)(A) receptors containing the α(2) subunit, 9-amino-2-cyclobutyl-5-(6-methoxy-2-methylpyridin-3-yl)-2,3-dihydro-1H-pyrrolo[3,4-b]quinolin-1-one (4) and 9-amino-2-cyclobutyl-5-(2-methoxypyridin-3-yl)-2,3-dihydro-1H-pyrrolo[3,4-b]quinolin-1-one (5), were radiolabelled at the methoxy position with carbon-11 (half-life=20.4 min). These quinolines represent a new class of potential radiotracers for imaging the benzodiazepine site of GABA(A) receptors with positron emission tomography (PET). Both radiotracers were reliably isolated following reaction of their respective pyridinone/pyridinol tautomeric precursors with [(11)C]CH(3)I in clinically useful, formulated quantities (2.9% and 2.7% uncorrected radiochemical yield, respectively, relative to [(11)C]CO(2)) with high specific activities (>70 GBq µ mol(-1); >2 Ci µ mol(-1)) and high radiochemical purities (>95%). The radiosyntheses reported herein represent rare examples of selectively isolating radiolabelled compounds bearing [(11)C]2-methoxypyridine moieties. Although both radiotracers demonstrated promising imaging characteristics based on preliminary ex vivo biodistribution studies in conscious rodents, higher brain uptake was observed with [(11)C]5 and therefore this radiotracer was further evaluated. Carbon-11 labelled 5 readily penetrated the brain (>1 standard uptake value in cortical regions at 15 min post-injection of the radiotracer), had an appropriate regional brain distribution for GABA(A) receptors that appeared to be reversible, and did not show any appreciable radiometabolites in rat brain homogenates up to 15 min post-injection. Preadministration of flumazenil (1, 10 mg kg(-1)) or 5 (5 mg kg(-1)) effectively blocked >50% of [(11)C]5 binding to the GABA(A) receptor-rich regions, thereby suggesting that this radiotracer is worthy of further evaluation for imaging GABA(A) receptors. Additionally (R,S)-N-(1-(3-chloro-4-methoxyphenyl)ethyl)-3,3-diphenylpropan-1-amine, 6, an allosteric modulator of GABA(B) receptors, was efficiently labelled in one step using [(11)C]methyl iodide. Ex vivo biodistribution studies in conscious rats showed low brain uptake, therefore, efforts are underway to discover alternative radiotracers to image GABA(B). In conclusion, [(11)C]5 is worthy of further evaluation in higher species for imaging GABA(A) receptors in the central nervous system.

Development of new radiopharmaceuticals for imaging monoamine oxidase B.

INTRODUCTION: Imaging monoamine oxidase B (MAO-B) in the central nervous system with PET is an important goal for psychiatric studies. We here report an improved and automated radiosynthesis of N-(6-[(18)F]-fluorohexyl)-N-methylpropargylamine ([(18)F]FHMP; [(18)F]-1), as well as the radiosynthesis of two new promising candidates for imaging cerebral MAO-B, namely, carbon-11-labeled 3-(4-[(11)C]-methoxyphenyl)-6-methyl-2H-1-benzopyran-2-one ([(11)C]-2) and N-((1H-pyrrol-2-yl)methyl)-N-[(11)C]-methyl-1-phenylmethanamine ([(11)C]-3). METHODS: Fluorine-18-labeled 1 was prepared via a tosyloxy precursor in 29%±5% uncorrected radiochemical yield, relative to [(18)F]-fluoride. Both carbon-11-labeled compounds were prepared with [(11)C]CH(3)I using the "LOOP" method in 11% and 18% uncorrected radiochemical yields, respectively, relative to starting [(11)C]CO(2). All radiotracers had specific activities >37 GBq/µmol and were >98% radiochemically pure at end of synthesis (<40 min). All radiotracers were evaluated by ex vivo biodistribution studies in conscious rodents. RESULTS: A major radioactive metabolite in the rodent brain was observed following administration of [(18)F]-1. While [(11)C]-2 had moderate brain penetration and good clearance from normal brain tissue, distribution of radioactivity in brain was indicative of free and nonspecific binding. Good brain uptake was observed with [(11)C]-3 (0.8%-1.4% injected dose per gram at 5 min postinjection), binding appeared to be reversible and distribution conformed with regional distribution of MAO-B in the rat brain. Preinjection of 3 or L-deprenyl showed a modest reduction (up to 25%) of brain activity. CONCLUSION: Carbon-11-labeled 3 was found to have the most favorable properties of the radiotracers evaluated; however, the signal-to-noise ratio was too low to warrant further in vivo imaging studies. Alternative radiotracers for imaging MAO-B are under development.

Comparisons of [18F]-1-deoxy-1-fluoro-scyllo-inositol with [18F]-FDG for PET imaging of inflammation, breast and brain cancer xenografts in athymic mice.

INTRODUCTION: The aim of the study was to evaluate the uptake of [(18)F]-1-deoxy-1-fluoro-scyllo-inositol ([(18)F]-scyllo-inositol) in human breast cancer (BC) and glioma xenografts, as well as in inflammatory tissue, in immunocompromised mice. Studies of [(18)F]-2-fluoro-2-deoxy-d-glucose ([(18)F]-FDG) under the same conditions were also performed. METHODS: Radiosynthesis of [(18)F]-scyllo-inositol was automated using a commercial synthesis module. Tumour, inflammation and normal tissue uptakes were evaluated by biodistribution studies and positron emission tomography (PET) imaging using [(18)F]-scyllo-inositol and [(18)F]-FDG in mice bearing subcutaneous MDA-MB-231, MCF-7 and MDA-MB-361 human BC xenografts, intracranial U-87 MG glioma xenografts and turpentine-induced inflammation. RESULTS: The radiosynthesis of [(18)F]-scyllo-inositol was automated with good radiochemical yields (24.6%±3.3%, uncorrected for decay, 65±2 min, n=5) and high specific activities (≥195 GBq/µmol at end of synthesis). Uptake of [(18)F]-scyllo-inositol was greatest in MDA-MB-231 BC tumours and was comparable to that of [(18)F]-FDG (4.6±0.5 vs. 5.5±2.1 %ID/g, respectively; P=.40), but was marginally lower in MDA-MB-361 and MCF-7 xenografts. Uptake of [(18)F]-scyllo-inositol in inflammation was lower than [(18)F]-FDG. While uptake of [(18)F]-scyllo-inositol in intracranial U-87 MG xenografts was significantly lower than [(18)F]-FDG, the tumour-to-brain ratio was significantly higher (10.6±2.5 vs. 2.1±0.6; P=.001). CONCLUSIONS: Consistent with biodistribution studies, uptake of [(18)F]-scyllo-inositol was successfully visualized by PET imaging in human BC and glioma xenografts, with lower accumulation in inflammatory tissue than [(18)F]-FDG. The tumour-to-brain ratio of [(18)F]-scyllo-inositol was also significantly higher than that of [(18)F]-FDG for visualizing intracranial glioma xenografts in NOD SCID mice, giving a better contrast.

Xe3OF3(+), a precursor to a noble-gas nitrate; syntheses and structural characterizations of FXeONO2, XeF2·HNO3, and XeF2·N2O4.

Xenon fluoride nitrate has been synthesized by reaction of NO(2)F with [FXeOXeFXeF][AsF(6)] at -50 °C. It was characterized in SO(2)ClF and CH(3)CN solutions by low-temperature (14)N, (19)F, and (129)Xe NMR spectroscopy and in the solid state by low-temperature Raman spectroscopy (-160 °C) and single-crystal X-ray diffraction (-173 °C). The reactions were carried out using natural abundance and (18)O-enriched [FXeOXeFXeF][AsF(6)] and (15)NO(2)F to aid in the vibrational assignments of FXeONO(2) and to establish the likely reaction pathway. Raman spectroscopy showed that FXe(16)ON((16)O(18)O) was formed, along with XeF(2) and [NO(2)][AsF(6)], when an excess of N(16)O(2)F reacted with [FXe(18)OXeFXeF][AsF(6)]. A reaction mechanism consistent with these findings is discussed. The crystal structure consists of well-separated FXeONO(2) molecules which display no significant intermolecular interactions, providing geometric parameters that are in good agreement with the gas-phase values determined from quantum-chemical calculations. Decomposition of solid FXeONO(2) is proposed to occur by three reaction pathways to give XeF(2), Xe, O(2), N(2)O(5), N(2)O(4), and NO(2)F. Attempts to synthesize FXeONO(2) and Xe(ONO(2))(2) by reaction of XeF(2) with HNO(3) in SO(2)ClF solution below -30 °C led to XeF(2)·HNO(3). The structure of XeF(2)·HNO(3) includes a hydrogen bond between HNO(3) and a fluorine atom of XeF(2), as well as an interaction between the xenon atom and an oxygen atom of HNO(3), leading to a crystal lattice comprised of layered sheets. A molecular addition compound between XeF(2) and N(2)O(4) crystallized from liquid N(2)O(4) below 0 °C. The crystal structure of XeF(2)·N(2)O(4) displayed weak interactions between the xenon atom of XeF(2) and the oxygen atoms of N(2)O(4). Quantum-chemical calculations have been used to assign the vibrational spectra of FXeONO(2), XeF(2)·HNO(3), and XeF(2)·N(2)O(4) and to better understand the nature of the interactions of HNO(3) and N(2)O(4) with XeF(2). The synthesis of [XeONO(2)][AsF(6)] was attempted by the reaction of FXeONO(2) with excess liquid AsF(5) between -78 and -50 °C, but resulted in slow formation of [NO(2)][AsF(6)], Xe, and O(2). Thermodynamic calculations show that the pathways to [XeONO(2)][AsF(6)] formation and decomposition are exothermic and spontaneous under standard conditions and at -78 °C.

NMR spectroscopic evidence for the intermediacy of XeF(3)(-) in XeF(2)/F(-) exchange, attempted syntheses and thermochemistry of XeF(3)(-) salts, and theoretical studies of the XeF(3)(-) anion.

The existence of the trifluoroxenate(II) anion, XeF(3)(-), had been postulated in a prior NMR study of the exchange between fluoride ion and XeF(2) in CH(3)CN solution. The enthalpy of activation for this exchange, ΔH(⧧), has now been determined by use of single selective inversion (19)F NMR spectroscopy to be 74.1 ± 5.0 kJ mol(-1) (0.18 M) and 56.9 ± 6.7 kJ mol(-1) (0.36 M) for equimolar amounts of [N(CH(3))(4)][F] and XeF(2) in CH(3)CN solvent. Although the XeF(3)(-) anion has been observed in the gas phase, attempts to prepare the Cs(+) and N(CH(3))(4)(+) salts of XeF(3)(-) have been unsuccessful, and are attributed to the low fluoride ion affinity of XeF(2) and fluoride ion solvation in CH(3)CN solution. The XeF(3)(-) anion would represent the first example of an AX(3)E(3) valence shell electron pair repulsion (VSEPR) arrangement of electron lone pair and bond pair domains. Fluorine-19 exchange between XeF(2) and the F(-) anion has also been probed computationally using coupled-cluster singles and doubles (CCSD) and density functional theory (DFT; PBE1PBE) methods. The energy-minimized geometry of the ground state shows that the F(-) anion is only weakly coordinated to XeF(2) (F(2)Xe---F(-); a distorted Y-shape possessing C(s) symmetry), while the XeF(3)(-) anion exists as a first-order transition state in the fluoride ion exchange mechanism, and is planar and Y-shaped (C(2v) symmetry). The molecular geometry and bonding of the XeF(3)(-) anion has been described and rationalized in terms of electron localization function (ELF) calculations, as well as the VSEPR model of molecular geometry. Quantum-chemical calculations, using the CCSD method and a continuum solvent model for CH(3)CN, accurately reproduced the transition-state enthalpy observed by (19)F NMR spectroscopy, and showed a negative but negligible enthalpy for the formation of the F(2)Xe---F(-) adduct in this medium.