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Stink bugs represent an increasing risk to soybean production in the Midwest region of the United States. The current sampling protocol for stink bugs in this region is tailored for population density estimation and thus is more relevant to research purposes. A practical decision-making framework with more efficient sampling effort for management of herbivorous stink bugs is needed. Therefore, a binomial sequential sampling plan was developed for herbivorous stink bugs in the Midwest region. A total of 146 soybean fields were sampled across 11 states using sweep nets in 2016, 2017, and 2018. The binomial sequential sampling plans were developed using combinations of five tally thresholds at two proportion infested action thresholds to identify those that provided the best sampling outcomes. Final assessment of the operating characteristic curves for each plan indicated that a tally threshold of 3 stink bugs per 25 sweeps, and proportion infested action thresholds of 0.75 and 0.95 corresponding to the action thresholds of 5 and 10 stink bugs per 25 sweeps, provided the optimal balance between highest probability of correct decisions (≥ 99%) and lowest probability of incorrect decisions (≤ 1%). In addition, the average sample size for both plans (18 and 12 sets of 25 sweeps, respectively) was lower than that for the other proposed plans. The binomial sequential sampling plan can reduce the number of sample units required to achieve a management decision, which is important because it can potentially reduce risk/cost of management for stink bugs in soybean in this region., (© The Author(s) 2021. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

Stink bugs (Hemiptera: Pentatomidae) are agricultural pests of increasing significance in the North Central Region of the United States, posing a threat to major crops such as soybean. Biological control can reduce the need for insecticides to manage these pests, but the parasitism of stink bugs by Tachinidae (Diptera) is poorly characterized in this region. The objective of this study was to evaluate the rate of parasitism of stink bugs by tachinids over 2 yr from nine states across the North Central Region. Parasitism was assessed by quantifying tachinid eggs on the integument of stink bug adults. Parasitism rates (i.e., percent of adult stink bugs with tachinid eggs) were compared across stink bug species, states, stink bug sex, and years. The mean percent parasitism of stink bugs by tachinids was about 6% across the region and did not differ among stink bug species. Mean percent parasitism was significantly higher in Missouri than in northern and western states. In addition, male stink bugs had significantly higher mean percent parasitism than females. Stink bug species commonly found in soybean in the region showed some parasitism and are therefore potentially vulnerable to oviposition by these parasitoids. This is the first study to characterize the level of parasitism of stink bugs by tachinids across the North Central Region., (© The Author(s) 2020. Published by Oxford University Press on behalf of Entomological Society of America.)

Background: Field-evolved pyrethroid resistance has been confirmed in western corn rootworm (WCR) populations collected from the United States (US) western Corn Belt. Resistance levels of WCR adults estimated in lab bioassays were confirmed to significantly reduce the efficacy of foliar-applied bifenthrin. The objective of the present study was to investigate the impact of WCR pyrethroid resistance levels on the performance of common soil-applied insecticide formulations (23.4% tefluthrin, 17.15% bifenthrin, and 0.1% cyfluthrin + 2.0% tebupirimphos). Field trials were conducted in 2016 and 2017 in three Nebraska, US, counties (Saunders, Clay, and Keith) where distinct levels of WCR susceptibility to pyrethroids (susceptible, moderately resistant, and highly resistant) had been previously reported in adult and larval bioassays., Results: All soil insecticide treatments effectively protected maize roots from a pyrethroid-susceptible WCR population at Saunders. In contrast, the efficacy of bifenthrin and tefluthrin soil insecticides was significantly reduced at Clay and Keith, where pyrethroid-resistant WCR populations were reported. At Keith, where an additional failure of the cyfluthrin + tebupirimphos soil insecticide was observed, WCR laboratory dose-response bioassays showed a consistent ∼5-fold resistance level to the active ingredients bifenthrin, tefluthrin, and cyfluthrin., Conclusion: The efficacy of common soil insecticides used in the US for WCR management was significantly reduced in populations exhibiting relatively low levels of WCR pyrethroid resistance. Using a multitactical approach to manage WCR within an integrated pest management framework may mitigate resistance evolution and prolong the usefulness of WCR insecticides within the system. © 2019 Society of Chemical Industry., (© 2019 Society of Chemical Industry.)

Stink bugs (Hemiptera: Pentatomidae) are an increasing threat to soybean (Fabales: Fabaceae) production in the North Central Region of the United States, which accounts for 80% of the country's total soybean production. Characterization of the stink bug community is essential for development of management programs for these pests. However, the composition of the stink bug community in the region is not well defined. This study aimed to address this gap with a 2-yr, 9-state survey. Specifically, we characterized the relative abundance, richness, and diversity of taxa in this community, and assessed phenological differences in abundance of herbivorous and predatory stink bugs. Overall, the stink bug community was dominated by Euschistus spp. (Hemiptera: Pentatomidae) and Chinavia hilaris (Say) (Hemiptera: Pentatomidae). Euschistus variolarius (Palisot de Beauvois) (Hemiptera: Pentatomidae), C. hilaris and Halyomorpha halys (Stål) (Hemiptera: Pentatomidae) were more abundant in the northwestern, southeastern and eastern parts, respectively, of the North Central Region of the United States. Economically significant infestations of herbivorous species occurred in fields in southern parts of the region. Species richness differed across states, while diversity was the same across the region. Herbivorous and predatory species were more abundant during later soybean growth stages. Our results represent the first regional characterization of the stink bug community in soybean fields and will be fundamental for the development of state- and region-specific management programs for these pests in the North Central Region of the United States., (© The Author(s) 2019. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

Stink bugs are an emerging threat to soybean (Fabales: Fabaceae) in the North Central Region of the United States. Consequently, region-specific scouting recommendations for stink bugs are needed. The aim of this study was to characterize the spatial pattern and to develop sampling plans to estimate stink bug population density in soybean fields. In 2016 and 2017, 125 fields distributed across nine states were sampled using sweep nets. Regression analyses were used to determine the effects of stink bug species [Chinavia hilaris (Say) (Hemiptera: Pentatomidae) and Euschistus spp. (Hemiptera: Pentatomidae)], life stages (nymphs and adults), and field locations (edge and interior) on spatial pattern as represented by variance-mean relationships. Results showed that stink bugs were aggregated. Sequential sampling plans were developed for each combination of species, life stage, and location and for all the data combined. Results for required sample size showed that an average of 40-42 sample units (sets of 25 sweeps) would be necessary to achieve a precision of 0.25 for stink bug densities commonly encountered across the region. However, based on the observed geographic gradient of stink bug densities, more practical sample sizes (5-10 sample units) may be sufficient in states in the southeastern part of the region, whereas impractical sample sizes (>100 sample units) may be required in the northwestern part of the region. Our findings provide research-based sampling recommendations for estimating densities of these emerging pests in soybean., (© The Author(s) 2019. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

A mild, regioselective, iridium-catalyzed C-H amidation and borylation of anthraquinones to the o-sulfonamide and m-borylated products has been developed. The anthraquinone carbonyl moieties direct the C-H amidation with high selectivity to afford the ortho-substituted products in modest to high yields.

A new method is tested in a single-blind study for detection, attribution, and quantification of methane emissions from the natural gas supply chain, which contribute substantially to annual U.S. emissions. The monitoring approach couples atmospheric methane concentration measurements from an open-path dual frequency comb laser spectrometer with meteorological data in an inversion to characterize emissions. During single-blind testing, the spectrometer is placed >1 km from decommissioned natural gas equipment configured with intentional leaks of controllable rate. Single, steady emissions ranging from 0 to 10.7 g min -1 (0-34.7 scfh) are detected, located, and quantified at three gas pads of varying size and complexity. The system detects 100% of leaks, including leaks as small as 0.96 g min -1 (3.1 scfh). It attributes leaks to the correct pad or equipment group (tank battery, separator battery, wellhead battery) 100% of the time and to the correct equipment (specific separator, tank, or wellhead) 67% of the time. All leaks are quantified to within 3.7 g min -1 (12 scfh); 94% are quantified to within 2.8 g min -1 (9 scfh). These tests are an important initial demonstration of the methodology's viability for continuous monitoring of large regions, with extension to other trace gases and industries.

Key Message: Evidence that supports a relation between AOX expression and improvement in plant height, internode length, and total leaf area under cool temperature is shown. Cell expansion and elongation appear to be enhanced when AOX expression was increased. Cotton growth is sensitive to cool temperature during germination and early seedling development. Delayed emergence, seedling damage, and increased risk to disease are common. Late seasonal cool weather is a major factor limiting the consistent production of high-quality cotton lint in West Texas. Alternative oxidase functions in the inner membrane of the mitochondria via an alternative respiration pathway and serves as a multifunctional system for amelioration of abiotic and biotic stresses. Cotton seedling emergence and growth exposed to cool temperatures was examined in plants with enhanced AOX expression. Thirteen T 1 seed lines showed 3 to 1 segregation for the T-DNA containing the tobacco AOX1 gene. Two over-expressing, single-copy, homozygous AOX lines (94-20 T and 66-6 T ) and Null line (94-3 N ) were selected for examination. The transcript levels were ≈ 2 to 6 fold higher in the AOX lines compared to those of the Null line and wild-type in stem, leaf, root and boll tissues. The research examined the hypothesis that transgenic cotton with enhanced AOX expression will have enhanced growth traits under suboptimal cool temperatures. Improved plant height, internode length, plant height and internode length from second node, and total leaf area under cool temperatures were observed in AOX over-expression lines. This may be attributed to improved cell expansion and elongation characteristics in the AOX line.

We present the first quantitative intercomparison between two open-path dual comb spectroscopy (DCS) instruments which were operated across adjacent 2-km open-air paths over a two-week period. We used DCS to measure the atmospheric absorption spectrum in the near infrared from 6021 to 6388 cm -1 (1565 to 1661 nm), corresponding to a 367 cm -1 bandwidth, at 0.0067 cm -1 sample spacing. The measured absorption spectra agree with each other to within 5×10 -4 without any external calibration of either instrument. The absorption spectra are fit to retrieve concentrations for carbon dioxide (CO 2 ), methane (CH 4 ), water (H 2 O), and deuterated water (HDO). The retrieved dry mole fractions agree to 0.14% (0.57 ppm) for CO 2 , 0.35% (7 ppb) for CH 4 , and 0.40% (36 ppm) for H 2 O over the two-week measurement campaign, which included 23 °C outdoor temperature variations and periods of strong atmospheric turbulence. This agreement is at least an order of magnitude better than conventional active-source open-path instrument intercomparisons and is particularly relevant to future regional flux measurements as it allows accurate comparisons of open-path DCS data across locations and time. We additionally compare the open-path DCS retrievals to a WMO-calibrated cavity ringdown point sensor located along the path with good agreement. Short-term and long-term differences between the two systems are attributed, respectively, to spatial sampling discrepancies and to inaccuracies in the current spectral database used to fit the DCS data. Finally, the two-week measurement campaign yields diurnal cycles of CO 2 and CH 4 that are consistent with the presence of local sources of CO 2 and absence of local sources of CH 4 ., Competing Interests: 2The use of trade names is necessary to specify the experimental results and does not imply endorsement by the National Institute of Standards and Technology. The authors declare that they have no conflict of interest.

Cotton exhibits moderately high vegetative tolerance to water-deficit stress but lint production is restricted by the available rainfed and irrigation capacity. We have described the impact of water-deficit stress on the genetic and metabolic control of fiber quality and production. Here we examine the association of tentative consensus sequences (TCs) derived from various cotton tissues under irrigated and water-limited conditions with stress-responsive QTLs. Three thousand sixteen mapped sequence-tagged-sites were used as anchored targets to examine sequence homology with 15,784 TCs to test the hypothesis that putative stress-responsive genes will map within QTLs associated with stress-related phenotypic variation more frequently than with other genomic regions not associated with these QTLs. Approximately 1,906 of 15,784 TCs were mapped to the consensus map. About 35% of the annotated TCs that mapped within QTL regions were genes involved in an abiotic stress response. By comparison, only 14.5% of the annotated TCs mapped outside these QTLs were classified as abiotic stress genes. A simple binomial probability calculation of this degree of bias being observed if QTL and non-QTL regions are equally likely to contain stress genes was P (x ≥ 85) = 7.99  × 10(-15). These results suggest that the QTL regions have a higher propensity to contain stress genes.

Key Message: Genetic improvements for many fiber traits are obtained by mutagenesis of elite cottons, mitigating genetic uniformity in this inbred polyploid by contributing novel alleles important to ongoing crop improvement. The elite gene pool of cotton (Gossypium spp.) has less diversity than those of most other major crops, making identification of novel alleles important to ongoing crop improvement. A total of 3,164 M5 lines resulting from ethyl methanesulfonate (EMS) mutagenesis of two G. hirsutum breeding lines, TAM 94L-25 and Acala 1517-99, were characterized for basic components of fiber quality and selected yield components. Across all measured traits, the ranges of phenotypic values among the mutant lines were consistently larger than could be explained by chance (5.27-10.1 for TAM 94 L-25 and 5.29-7.94 standard deviations for Acala 1517-99-derived lines). Multi-year replicated studies confirmed a genetic basis for these differences, showing significant correlations between lines across years and environments. A subset of 157 lines selected for superior fiber qualities, including fiber elongation (22 lines), length (22), lint percent (17), fineness (23), Rd value (21), strength (19), uniformity (21) and multiple attributes in a selection index (26) were compared to 55 control lines in replicated trials in both Texas and Georgia. For all traits, mutant lines showing substantial and statistically significant improvements over control lines were found, in most cases from each of the two genetic backgrounds. This indicates that genetic improvements for a wide range of fiber traits may be obtained from mutagenesis of elite cottons. Indeed, lines selected for one fiber trait sometimes conferred additional attributes, suggesting pleiotropic effects of some mutations and offering multiple benefits for the incorporation of some alleles into mainstream breeding programs.

Polyploidy often confers emergent properties, such as the higher fibre productivity and quality of tetraploid cottons than diploid cottons bred for the same environments. Here we show that an abrupt five- to sixfold ploidy increase approximately 60 million years (Myr) ago, and allopolyploidy reuniting divergent Gossypium genomes approximately 1-2 Myr ago, conferred about 30-36-fold duplication of ancestral angiosperm (flowering plant) genes in elite cottons (Gossypium hirsutum and Gossypium barbadense), genetic complexity equalled only by Brassica among sequenced angiosperms. Nascent fibre evolution, before allopolyploidy, is elucidated by comparison of spinnable-fibred Gossypium herbaceum A and non-spinnable Gossypium longicalyx F genomes to one another and the outgroup D genome of non-spinnable Gossypium raimondii. The sequence of a G. hirsutum A(t)D(t) (in which 't' indicates tetraploid) cultivar reveals many non-reciprocal DNA exchanges between subgenomes that may have contributed to phenotypic innovation and/or other emergent properties such as ecological adaptation by polyploids. Most DNA-level novelty in G. hirsutum recombines alleles from the D-genome progenitor native to its New World habitat and the Old World A-genome progenitor in which spinnable fibre evolved. Coordinated expression changes in proximal groups of functionally distinct genes, including a nuclear mitochondrial DNA block, may account for clusters of cotton-fibre quantitative trait loci affecting diverse traits. Opportunities abound for dissecting emergent properties of other polyploids, particularly angiosperms, by comparison to diploid progenitors and outgroups.

Proposed electrocatalytic proton reduction intermediates of hydrogenase mimics were synthesized, observed, and studied computationally. A new mechanism for H(2) generation appears to involve Fe(2)(CO)(6)(1,2-S(2)C(6)H(4)) (3), the dianions {[1,2-S(2)C(6)H(4)][Fe(CO)(3)(μ-CO)Fe(CO)(2)](2-) (3(2-)), the bridging hydride {[1,2-S(2)C(6)H(4)][Fe(CO)(3)(μ-CO)(μ-H)Fe(CO)(2)]}(-), 3H(-)(bridging), and the terminal hydride 3H(-)(term-stag), {[1,2-S(2)C(6)H(4)][HFe(CO)(3)Fe(CO)(3)]}(-), as intermediates. The dimeric sodium derivative of 3(2-), {[Na(2)(THF)(OEt(2))(3)][3(2-)]}(2) (4) was isolated from reaction of Fe(2)(CO)(6)(1,2-S(2)C(6)H(4)) (3) with excess sodium and was characterized by X-ray crystallography. It possesses a bridging CO and an unsymmetrically bridging dithiolate ligand. Complex 4 reacts with 4 equiv. of triflic or benzoic acid (2 equiv. per Fe center) to generate H(2) and 3 in 75% and 60% yields, respectively. Reaction of 4 with 2 equiv. of benzoic acid generated two hydrides in a 1.7 : 1 ratio (by (1)H NMR spectroscopy). Chemical shift calculations on geometry optimized structures of possible hydride isomers strongly suggest that the main product, 3H(-)(bridging), possesses a bridging hydride ligand, while the minor product is a terminal hydride, 3H(-)(term-stag). Computational studies support a catalytic proton reduction mechanism involving a two-electron reduction of 3 that severs an Fe-S bond to generate a dangling thiolate and an electron rich Fe center. The latter iron center is the initial site of protonation, and this event is followed by protonation at the dangling thiolate to give the thiol thiolate [Fe(2)H(CO)(6)(1,2-SHSC(6)H(4))]. This species then undergoes an intramolecular acid-base reaction to form a dihydrogen complex that loses H(2) and regenerates 3.

Soil biotic and abiotic factors strongly influence nitrogen (N) availability and increases in nitrification rates associated with the application of manure. In this study, we examine the effects of edaphic properties and a dairy (Bos taurus) slurry amendment on N availability, nitrification rates and nitrifier communities. Soils of variable texture and clay mineralogy were collected from six USDA-ARS research sites and incubated for 28 d with and without dairy slurry applied at a rate of ~300 kg N ha(-1). Periodically, subsamples were removed for analyses of 2 M KCl extractable N and nitrification potential, as well as gene copy numbers of ammonia-oxidizing bacteria (AOB) and archaea (AOA). Spearman coefficients for nitrification potentials and AOB copy number were positively correlated with total soil C, total soil N, cation exchange capacity, and clay mineralogy in treatments with and without slurry application. Our data show that the quantity and type of clay minerals present in a soil affect nitrifier populations, nitrification rates, and the release of inorganic N. Nitrogen mineralization, nitrification potentials, and edaphic properties were positively correlated with AOB gene copy numbers. On average, AOA gene copy numbers were an order of magnitude lower than those of AOB across the six soils and did not increase with slurry application. Our research suggests that the two nitrifier communities overlap but have different optimum environmental conditions for growth and activity that are partly determined by the interaction of manure-derived ammonium with soil properties., (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)

Seventeen backcross-self families from crosses between two Gossypium hirsutum recurrent parent lines (CA3084, CA3093) and G. tomentosum were used to identify quantitative trait loci (QTLs) controlling fiber quality traits. A total of 28 QTLs for fiber quality traits were identified (P < 0.001), including four for fiber elongation, eight for fiber fineness, four for fiber length, four for fiber strength, six for fiber uniformity, one for boll weight, and one for boll number. Three statistically significant marker-trait associations for lint yield were found in a single environment, but need further validation. Two-way analysis of variance revealed one locus with significant genotype × family interaction (P < 0.001) for fiber strength and a second locus with significant genotype × environment interaction (P < 0.001) in the CA3084 background, and two loci with significant genotype × background interaction (P < 0.001) for the 28 common markers segregating in both of the two recurrent backgrounds. Co-location of many QTLs for fiber quality traits partially explained correlations among these traits. Some G. tomentosum alleles were associated with multiple favorable effects, offering the possibility of rapid genetic gain by introgression. Many G. tomentosum alleles were recalcitrant to homozygosity, suggesting that they might be most effectively deployed in hybrid cottons. DNA markers linked to G. tomentosum QTLs identified in the present study promise to assist breeders in transferring and maintaining valuable traits from this exotic source during Upland cotton cultivar development. This study also adds further evidence to prior studies indicating that the majority of genetic variation associated with fiber quality in tetraploid cotton traces to the D-subgenome from a diploid ancestor that does not produce spinnable fiber.

Growth, yield, and yield quality of cotton are greatly affected by water-deficit stress. We have identified the genes and associated metabolic pathways involved in the water-deficit stress response in leaf and root. Gene expression profiles were developed for leaf and root tissues subjected to slow-onset water deficit under controlled, glasshouse conditions. The water-deficit stress was characterized by leaf water potential of -23.1 bars for stressed tissue compared to -8.7 bars for fully-irrigated control plants and a corresponding decrease in net carbon assimilation to approximately 60% of the rates seen in the irrigated controls (30.3 ± 4.7 μmol CO(2) m(-2) s(-1) compared to 17.8 ± 5.9 μmol CO(2) m(-2) s(-1)). Profiling experiments revealed 2,106 stress-responsive transcripts, 879 classified as stress-induced, 1,163 stress-repressed, and 64 showed reciprocal expression patterns in root and leaf. The majority of stress-responsive transcripts had tissue-specific expression patterns and only 173 genes showed similar patterns of stress responsive expression in both tissues. A variety of putative metabolic and regulatory pathways were identified using MapMan software and the potential targets for candidate gene selection and ectopic expression to alter these pathways and responses are discussed.

Understanding the bonding of sulfur at the germanium surface is important to developing good passivation routes for germanium-based electronic devices. The adsorption behavior of ethyl disulfide (EDS) and 1,8-naphthalene disulfide (NDS) at the Ge(100)-2 × 1 surface has been studied under ultrahigh vacuum conditions to investigate both their fundamental reactivity and their effectiveness as passivants of this surface. X-ray photoelectron spectroscopy, multiple internal reflection-infrared spectroscopy, and density functional theory results indicate that both molecules adsorb via S-S dissociation at room temperature. Upon exposure to ambient air, the thiolate adlayer remains intact for both EDS- and NDS-functionalized surfaces, indicating the stability of this surface attachment. Although both systems resist oxidation compared to the bare Ge(100)-2 × 1 surface, the Ge substrate is significantly oxidized in all cases (17-57% relative to the control), with the NDS-passivated surface undergoing up to two times more oxidation than the EDS-passivated surface at the longest air exposure times studied. The difference in passivation capability is attributed to the difference in surface coverage on Ge(100)-2 × 1, where EDS adsorption leads to a saturation coverage 17% higher than that for NDS/Ge(100)-2 × 1.

The solvent-free reaction of M{N(SiMe(3))(2)}(2) (M = Ge, Sn, or Pb) with the sterically encumbered primary amine 2,6-dimesitylaniline Ar(#)NH(2) [Ar(#) = C(6)H(3)-2,6(C(6)H(2)-2,4,6-Me(3))(2)] at ca. 165-175 degrees C afforded the highly colored imido dimers {M(mu-NAr(#))}(2), where M = Ge (1), Sn (2), or Pb (3), with disilylamine elimination. The compounds were characterized by single-crystal X-ray crystallography and heteronuclear NMR spectroscopy. The structures of 1-3 were very similar and had nonplanar four-membered M(2)N(2) ring cores that are folded along the M---M axis. The nitrogen atoms are planar-coordinated, and the M-N distances are consistent with single bonding. The reaction of M{N(SiMe(3))(2)}(2) with Ar(#)NH(2) in a 2:1 ratio in solution at lower temperature afforded the relatively stable monomeric primary amido species M{N(H)Ar(#)}(2), where M = Ge (4), Sn (5), or Pb (6). Complexes 4-6 displayed V-shaped MN(2) structures, and 5 and 6 revealed close approaches between the metal atom and ipso-carbon atoms of two flanking Mes groups of the terphenyl substituents [Sn(II)---C (2.957 A) and Pb(II)---C (2.965 A)]. The secondary metal-ligand interactions exerted large effects on their electronic and NMR spectra.

The timing of application for the management of rangeland grasshoppers (Orthoptera: Acrididae) is critical, especially as insecticides become more specialized and the use of Insect Growth Regulators becomes more widespread. The general seasonal occurrence of adults of many grasshopper species has been well documented; however, their appearance varies widely between years. We analyzed sweep samples collected over the western two thirds of Nebraska from a 3-yr period and noted the occurrence of adults by region for eight species of rangeland grasshoppers. We analyzed occurrence based on degree-day accumulations for the region and developed estimates of degree-day requirements for these species. Because these grasshopper species are common rangeland pests, degree-day requirements to reach adulthood should improve the effectiveness of grasshopper treatment programs over a large geographic area.

The diiron complexes [Fe(2)(CO)(6)(1,8-S(2)-2,4,5,7-Cl(4)C(10)H(2))] (3), [Fe(2)(CO)(6)(1,8-S(2)C(10)H(6))] (4), and [Fe(2)(CO)(6)(1,8-S(2)-2,7-tBu(2)C(10)H(4))] (5) were synthesized in moderate yield from naphthalene-1,8-dithiols and [Fe(3)(CO)(12)]. They were characterized by IR, (1)H and (13)C NMR spectroscopy and 3 and 4 were characterized by X-ray crystallography. They contain a butterfly Fe(2)S(2) core with Fe-Fe distances of 2.529(1) (3) and 2.506(1) A (4). Cyclic voltammetry (CH(2)Cl(2)/nBu(4)PF(6)) revealed two one-electron reductions, at potentials more positive than those for the related [Fe(2)(CO)(6)(S(CH(2))(3)S)] (1), and one one-electron oxidation. The first reduction of the electron poor 3 (-1.60 V vs Fc/Fc(+)) is 240 mV more positive than the first reduction of the electron rich 5 (-1.84 V). Electrochemical studies revealed that 3-5 facilitate the proton reduction of p-toluenesulfonic acid. The rates of catalysis, with a 95% confidence limit, are 2.4+/-0.8 (1), 5.2+/-0.8 (3), 3.1+/-1.1 (4), 2.9+/-0.6 (5), and 4.5+/-0.2 h(-1) for the related [Fe(2)(CO)(6)(1,2-S(2)C(6)H(4))]. The rates were determined by bulk electrolysis at -1.70 V (Fc/Fc(+)), which correspond to an overpotential of 1.05 V for p-toluenesulfonic acid.

Black root rot (BRR), incited by the soilborne pathogen Thielaviopsis basicola has the potential to cause significant economic loss in cotton (Gossypium spp.) production. Cultivated tetraploids of cotton (G. hirsutum and G. barbadense) are susceptible although resistant types have been identified in a possible tetraploid progenitor, G. herbaceum. Genetic mapping was used to detect the chromosomal locations of quantitative trait loci (QTL) that confer resistance to the BRR pathogen. A population of F(2) individuals (G. herbaceum x G. arboreum) and F(2:3) progeny families were examined. Phenotypic variation between resistant and susceptible reactions could be explained partly by three QTL. The BRR5.1, BRR9.1, and BRR13.1 QTL each explained 19.1, 10.3 and 8.5% of the total phenotypic variation, respectively. The combination of all three in a single genetic model explained 32.7% of the phenotypic variation. Comparative analysis was conducted on significant QTL regions to deduce the cotton-Arabidopsis synteny relationship and examine the correspondence between BRR QTL and Arabidopsis pathogen defense genes. Totally 20 Arabidopsis synteny segments corresponded within one of three BRR QTL regions. Each synteny segment contains many potential Arabidopsis candidate genes. A total of 624 Arabidopsis genes, including 22 pathogen defense and 36 stress response genes, could be placed within the syntenic regions corresponding to the BRR QTL. Fine mapping is needed to delineate each underlying BRR R-gene and possible Arabidopsis orthologs. Research and breeding activities to examine each QTL and underlying genes in Upland cotton (G. hirsutum) are ongoing.

The synthesis and structural characterization of the first homologous, molecular M-M bonded series for the group 12 metals are reported. The compounds Ar'MMAr' (M = Zn, Cd, or Hg; Ar' = C(6)H(3)-2,6-(C(6)H(3)-2,6-Pr(i)(2))(2)) were synthesized by reduction of the corresponding arylmetal halides by alkali metal/graphite (Zn or Hg) or sodium hydride (Cd). These compounds possess almost linear C-M-M-C core structures with two-coordinate metals. The observed M-M bonds distances were 2.3591(9), 2.6257(5), and 2.5738(3) A for the zinc, cadmium, and mercury species, respectively. The shorter Hg-Hg bond in comparison to that of Cd-Cd is consistent with DFT calculations which show that the strength of the Hg-Hg bond is greater. The arylmetal halides precursors (Ar'MI)(1 or 2), and the highly reactive hydrides (Ar'MH)(1 or 2), were also synthesized and fully characterized by X-ray crystallography (Zn and Cd) and multinuclear NMR spectroscopy. The arylzinc and arylcadmium iodides have iodide-bridged dimeric structures, whereas the arylmercury iodide, Ar'HgI, is monomeric. The arylzinc and arylcadmium hydrides have symmetric (Zn) or unsymmetric (Cd) mu-H-bridged structures. The Ar'HgH species was synthesized and characterized by spectroscopy, but a satisfactory refinement of the structure was precluded by the contamination of monomeric Ar'HgH by Ar'H. It was also shown that the decomposition of Ar'Cd(mu-H)(2)CdAr' at room temperature leads to the M-M bonded Ar'CdCdAr', thereby supporting the view that the reduction of the iodide proceeds via the hydride intermediate.

QTL mapping experiments yield heterogeneous results due to the use of different genotypes, environments, and sampling variation. Compilation of QTL mapping results yields a more complete picture of the genetic control of a trait and reveals patterns in organization of trait variation. A total of 432 QTL mapped in one diploid and 10 tetraploid interspecific cotton populations were aligned using a reference map and depicted in a CMap resource. Early demonstrations that genes from the non-fiber-producing diploid ancestor contribute to tetraploid lint fiber genetics gain further support from multiple populations and environments and advanced-generation studies detecting QTL of small phenotypic effect. Both tetraploid subgenomes contribute QTL at largely non-homeologous locations, suggesting divergent selection acting on many corresponding genes before and/or after polyploid formation. QTL correspondence across studies was only modest, suggesting that additional QTL for the target traits remain to be discovered. Crosses between closely-related genotypes differing by single-gene mutants yield profoundly different QTL landscapes, suggesting that fiber variation involves a complex network of interacting genes. Members of the lint fiber development network appear clustered, with cluster members showing heterogeneous phenotypic effects. Meta-analysis linked to synteny-based and expression-based information provides clues about specific genes and families involved in QTL networks.

Reactions of the "digallene" Ar'GaGaAr'(1) (Ar' = C(6)H(3)-2,6-(C(6)H(3)-2,6-Pr(i)(2))(2)), which dissociates to green :GaAr' monomers in solution, with unsaturated N-N-bonded molecules are described. Treatment of solutions of :GaAr' with the bulky azide N(3)Ar(#) (Ar(#) = C(6)H(3)-2,6-(C(6)H(2)-2,6-Me(2)-4-Bu(t))(2)), afforded the red imide Ar'GaNAr(#) (2). Addition of the azobenzenes, ArylNNAryl (Aryl = C(6)H(4)-4-Me (p-tolyl), mesityl, and C(6)H(3)-2,6-Et(2)) yielded the 1,2-Ga(2)N(2) ring compound Ar'GaN(p-tolyl)N(p-tolyl)GaA' (3) or the products MesN=NC(6)H(2)-2,4-Me(2)-6-Ga(Me)Ar' (4) and 2,6-Et(2)C(6)H(3)N=NC(6)H(3)-2-Et-6-Ga(Et)Ar' (5). Reaction of GaAr' with N(2)CPh(2) yielded the 1,3-Ga(2)N(2) ring compound Ar'Ga(mu:eta(1)-N(2)CPh(2))(2)GaAr' (6), which is quasi-isomeric to 3. Calculations on simple model isomers showed that the Ga(I) amide GaNR(2) (R = Me) is much more stable than the isomeric Ga(III) imide RGaNR. This led to the synthesis of the first stable monomeric Ga(I) amide, GaN(SiMe(3))Ar' ' (8) (Ar' ' = C(6)H(3)-2,6-(C(6)H(2)-2,4,6-Me(3))(2) from the reaction of LiN(SiMe(3))Ar' ' (7) and "GaI". Compound 8 is also the first one-coordinate gallium species to be characterized in the solid state. The reaction of 8 with N(3)Ar' ' afforded the amido-imide derivative Ar' 'NGaN(SiMe(3))Ar' ' (9), a gallium nitrogen analogue of an allyl anion. All compounds were spectroscopically and structurally characterized. In addition, DFT calculations were performed on model compounds of the amide, imide, and cyclic 1,2- and 1,3-species to better understand their bonding. The pairs of compounds 2 and 8 as well as 3 and 6 are rare examples of quasi-isomeric heavier main group element compounds.

We validated a stochastic model of the evolution of resistance to adulticidal sprays of methyl-parathion in western corn rootworm, Diabrotica virgifera virgifera LeConte, populations in Nebraska. The population dynamics predicted by the model resembled that reported for field populations, and time until control failures occurred closely matched reports by commercial crop consultants. We incorporated uncertainty about the values used for 18 model parameters by replacing default values with random draws taken from a normal distribution. One parameter, the initial resistance allele frequency, was no longer measurable because of the evolution of resistance. We therefore proposed five candidate initial allele frequencies and developed probability distributions for the time to resistance for each by running 1000 simulations with parameters randomly varied. These distributions included variation because of stochastic effects as well as parameter uncertainty. We used Bayesian inference to estimate the candidate frequency most likely, given reported times to field control failures. The initial allele frequency of 10(-4) was most likely (29%), 10(-3) was less likely (28%), whereas 10(-6) was relatively unlikely (5%). Results from sensitivity analysis depended upon how evolution of resistance was measured. When resistance was examined as a genetic phenomenon, the rate of increase of the resistance allele depended almost entirely on genetic factors (LC50 values), the characteristics of the pesticide (residual activity), and the variance associated with emergence of adults. When resistance was measured as failure of methyl-parathion to reduce populations below threshold levels (0.5 gravid females per plant), parameters that contributed to population growth rate (mortality and fecundity) were also important. These data suggest two important phases in resistance evolution in corn rootworms: a genetic phase associated with negative growth rates and rapid changes in resistance allele frequencies and a rebound phase associated with positive growth rates and near fixation of the resistance allele.

A new series of Fe(II) complexes, FeCl2[N(R)=C(Me)C(Me)=N(R)], containing diimine ligands with hemilabile sidearms R (R = CH2(CH2)2NMe2, 1, CH2(CH2)2OMe, 2, CH2(CH2)2SMe), 3) were synthesized. The crystal structure of 1 showed 6-coordination where both amine arms were attached, whereas 2 was a 5-coordinate 16e species with one methoxy arm dangling free. Extensive attempts were made to bind CO to these species to synthesize precursors for dihydrogen complexes but were unsuccessful. Reaction of 1 with 1 or 2 equiv of AgOTf under CO atmosphere resulted in isolation of only a 6-coordinate bis(triflate)-containing product [Fe[N(R)=C(Me)C(Me)=N(R)](OTf)2] (R = CH2(CH2)2NMe2), 5. Reaction of 5-coordinate 2 with AgSbF6 under CO did not give a CO adduct but afforded instead a dicationic dinuclear complex [Fe[N(R)=C(Me)C(Me)=N(R)](mu-Cl)]2[SbF6]2 (R = CH2(CH2)2OMe), 4, containing a weakly bound SbF6. Thus coordination of hard-donor anions to iron was favored over CO binding. The unexpected rejection of binding of CO is rationalized by the iron being in a high-spin state in this system and energetically incapable of spin crossover to a low-spin state. Theoretical calculations on CO interaction with Fe(II) centers in spin states S = 0, 1, and 2 for both the 16e complexes and their CO adducts aid further understanding of this problem. They show that interaction of CO with a high-spin 5-coordinate Fe model diimine complex is essentially thermoneutral but is exergonic by about 48 kcal/mol to a comparable but low-spin diphosphine fragment. Spin crossover is thus disfavored thermodynamically rather than kinetically (e.g. a "spin block" effect); i.e., the ligand field strengths of the primarily N-donor groups are apparently insufficient to give a low-spin CO adduct.

Relative flight behavior of methyl-parathion-resistant and -susceptible western corn rootworm, Diabrotica virgifera virgifera LeConte populations, was studied as part of a larger effort to characterize the potential impact of insecticide resistance on adult life history traits and to understand the evolution and spread of resistance. A computer interfaced actograph was used to compare flight of resistant and susceptible individuals, and flight of resistant individuals with and without prior exposure to methyl-parathion. In each case, mean trivial and sustained flight durations were compared among treatments. In general, there were few differences in trivial or sustained flight characteristics as affected by beetle population, insecticide exposure, sex, or age and there were few significant interactions among variables. Tethered flight activity was highly variable and distributions of flight duration were skewed toward flights of short duration. Tethered flight activity was similar among resistant and susceptible beetles with the exception that susceptible beetles initiated more flights per beetle than resistant beetles. After sublethal exposure to methyl-parathion, total flight time, total trivial flight time, and mean number of flights per resistant beetle declined significantly. Because long-range flight was uncommon, short- to medium-duration flights may play an important role in determining gene flow and population spread of resistant D. v. virgifera. These results suggest that organophosphate-resistant beetles can readily move and colonize new areas, but localized selection pressure (e.g., management practices) and exposure to methyl-parathion may contribute to the small-scale differences in resistance intensity often seen in the field.

Reaction of TlCl and [LiN(Me)Ar(Mes)2](2) [Ar(Mes)2 = C(6)H(3)-2,6-(C(6)H(2)-2,4,6-Me(3))(2)] in Et(2)O generated the thallium amide, TlN(Me)Ar(Mes)2 (1). X-ray data showed that it has a monomeric structure with an average Tl-N distance of 2.364(3) Angstroms. There was also a Tl-arene approach [Tl-centroid = 3.026(2) Angstroms (avg)] to a flanking mesityl ring from the terphenyl substituent. DFT calculations showed that this interaction is weak and supported essentially one coordination for thallium. The electronic spectrum of 1 is hypsochromically shifted in comparison to the monomeric TlAr(Trip)2 (Trip = C(6)H(2)-2,4,6-Pr(i)(3)).

The synthesis and characterization of three new organothallium(I) compounds are reported. Reaction of (Ar'Li)(2) (Ar' = C(6)H(3)-2,6-(C(6)H(3)-2,6-Pr(i)(2))(2)) and Ar"Li (Ar" = C(6)H(3)-2,6-(C(6)H(3)-2,6-Me(2))(2)) with TlCl in Et(2)O afforded (Ar'Tl)(2) (1) and (Ar' 'Tl)(3) (2). The "dithallene" 1 is the heaviest group 13 dimetallene and features a planar, trans-bent structure with Ar'Tl-Tl = 119.74(14) degrees and Tl-Tl = 3.0936(8) A. Compound 2 is the first structurally characterized neutral, three-membered ring species of formula c-(MR)(3) (M = Al-Tl; R = organo group). The Tl(3) ring has Tl-Tl distances in the range ca. 3.21-3.37 A as well as pyramidal Tl geometries. The Tl-Tl bonds in 1 and 2 are outside the range (2.88-2.97 A) of Tl-Tl single bonds in R(2)TlTlR(2) compounds. The weak Tl-Tl bonding in 1 and 2 leads to their dissociation into Ar'Tl and Ar' 'Tl monomers in hexane. The Ar'Tl monomer behaves as a Lewis base and readily forms a 1:1 donor-acceptor complex with B(C(6)F(5))(3) to give Ar'TlB(C(6)F(5))(3), 3. Adduct 3 features an almost linear thallium C(ipso)-Tl-B angle of 174.358(7) degrees and a Tl-B distance of 2.311(2) A, which indicates strong association. Treatment of 1 with a variety of reagents resulted in no reactions. The lower reactivity of 1 is in accord with the reluctance of Tl(I) to undergo oxidation to Tl(III) due to the unreactive character of the 6s(2) electrons.

Interactions of the parasitoid Lysiphlebus testaceipes (Cresson) and the greenbug, Schizaphis graminum (Rondani), on greenbug-resistant 'Cargill 607E' (antibiosis), 'Cargill 797' (primarily tolerance), and -susceptible 'Golden Harvest 510B' sorghum, Sorghum bicolor (L.) Moench, were tested using three levels of biotype I greenbug infestation. The parasitoid infestation rate was 0.5 female and 1.0 male L. testaceipes per plant. For all three greenbug infestation levels, the parasitoid brought the greenbug under control (i.e., prevented the greenbugs from killing the plants) on both resistant hybrids, but it did not prevent heavy leaf damage at the higher greenbug infestation rates. At the low greenbug infestation rate (50 greenbugs per resistant plant when parasitoids were introduced), greenbugs damaged 5 and 18% of the total leaf area on 'Cargill 797' and 'Cargill 607E', respectively, before greenbugs were eliminated. Leaf damage was higher for the intermediate infestation study (120 greenbugs per plant), 21% and 30% leaf area were damaged on the resistant sorghum hybrids 'Cargill 797' and 'Cargill 607E', respectively. At the high greenbug infestation rate (300 greenbugs per plant), heavy damage occurred: 61% on 'Cargill 607E' and 75% on 'Cargill 797'. The parasitoids did not control greenbugs on the susceptible sorghum hybrid 'Golden Harvest 510B'. L. testaceipes provided comparable control on both greenbug-resistant hybrids. This study supports previous studies indicating that L. testaceipes is effective in controlling greenbugs on sorghum with antibiosis resistance to greenbugs. Furthermore, new information is provided indicating that L. testaceipes is also effective in controlling greenbugs on a greenbug-tolerant hybrid.

The reaction of PbBr(2) with the lithium reagents LiC(6)H(3)-2,6-(C(6)H(3)-2,6-Pr(i)(2))(2) (LiArPr(i)(2)) and Et(2)O.LiC(6)H(3)-2,6-(2,6-Pr(i)-4-Bu(t)C(6)H(2))(2) (Et(2)O.LiArPr(i)(2)Bu(t)) furnished the bromide bridged organolead(II) halides [Pb(mu-Br)ArPr(i)(2)](2) (1) and[Pb(mu-Br)ArPr(i)(2)Bu(t)](2) (2) as orange crystals. Treatment of 1 with a stoichiometric amount of methylmagnesium bromide resulted in the "diplumbene" Pr(i)(2)Ar(Me)PbPb(Me)ArPr(i)(2) (3). The addition of 1 equiv of 4-tert-butylphenylmagnesium bromide to 1 afforded the feebly associated, Pb-Pb bonded species [Pb(C(6)H(4)-4-Bu(t))ArPr(i)(2)](2) (4), whereas the corresponding reaction of tert-butylmagnesium chloride and 1 afforded the monomer Pb(Bu(t))ArPr(i)(2) (5). The reaction of the more crowded aryl lead(II) bromide [Pb(mu-Br)ArPr(i)(3)](2) (Ar = C(6)H(3)-2,6(C(6)H(2)-2,4,6-Pr(i)(3))(2)) with 4-isopropyl-benzylmagnesium bromide or LiSi(SiMe(3))(3) yielded the monomers 6, [Pb(CH(2)C(6)H(4)-4-Pr(i))ArPr(i)(3)], or 7, [Pb(Si(SiMe(3))(3))ArPr(i)(3)]. All compounds were characterized with use of X-ray crystallography, (1)H, (13)C, and (207)Pb NMR (3-7), and UV-vis spectroscopy. The dimeric Pb-Pb bonded (Pb-Pb = 3.1601(6) A) structure of 3 may be contrasted with the previously reported monomeric structure of Pb(Me)ArPr(i)(3), which differs from 3 only in that it has para Pr(i) substituents on the flanking aryl rings. The presence of these groups is sufficient to prevent the weak Pb-Pb bonding seen in 3. The dimer 4 displays a Pb-Pb distance of 3.947(1) A, which indicates a very weak lead-lead interaction, and it is possible that this close approach could be caused by packing effects. The monomeric structures of 6 and 7 are attributable to steric effects and, in particular, to the large size of ArPr(i)(3).

We report genetic maps for diploid (D) and tetraploid (AtDt) Gossypium genomes composed of sequence-tagged sites (STS) that foster structural, functional, and evolutionary genomic studies. The maps include, respectively, 2584 loci at 1.72-cM ( approximately 600 kb) intervals based on 2007 probes (AtDt) and 763 loci at 1.96-cM ( approximately 500 kb) intervals detected by 662 probes (D). Both diploid and tetraploid cottons exhibit negative crossover interference; i.e., double recombinants are unexpectedly abundant. We found no major structural changes between Dt and D chromosomes, but confirmed two reciprocal translocations between At chromosomes and several inversions. Concentrations of probes in corresponding regions of the various genomes may represent centromeres, while genome-specific concentrations may represent heterochromatin. Locus duplication patterns reveal all 13 expected homeologous chromosome sets and lend new support to the possibility that a more ancient polyploidization event may have predated the A-D divergence of 6-11 million years ago. Identification of SSRs within 312 RFLP sequences plus direct mapping of 124 SSRs and exploration for CAPS and SNPs illustrate the "portability" of these STS loci across populations and detection systems useful for marker-assisted improvement of the world's leading fiber crop. These data provide new insights into polyploid evolution and represent a foundation for assembly of a finished sequence of the cotton genome.

Reduction of Ar'AlI2 (Ar' = Ar'= C6H3-2,6-Dipp2; Dipp = C6H3-2,6-Pri2) with KC8 in diethyl ether most probably affords the first "dialuminene", Ar'AlAlAr'; it was characterized by its reaction with toluene which yielded a [2 + 4] cycloaddition product incorporating the Ar'AlAlAr' unit.

The synthesis, structure, and properties of several new organogallium(I) compounds are reported. The monovalent compounds GaAr* (Ar* = C(6)H(3)-2,6-Trip(2), Trip = C(6)H(2)-2,4,6-Pr(i)()(3), 1), GaAr# (Ar# = C(6)H(3)-2,6(Bu(t)Dipp)(2), Bu(t)Dipp = C(6)H(2)-2,6-Pr(i)(2)-4-Bu(t)(), 4), and the dimeric (GaAr')(2) (Ar' = C(6)H(3)-2,6-Dipp(2), Dipp = C(6)H(3)-2,6-Pr(i)(2), 6) were synthesized by the reaction of "GaI" with (Et(2)O)LiAr*, (Et(2)O)LiAr# (3), or (LiAr')(2). Compounds 1 and 4 were isolated as green crystals, whereas 6 was obtained as a brown-red crystalline solid. All three compounds dissolved in hydrocarbon solvents to give green solutions and almost identical UV/visible spectra. Cryoscopy of 1 and 6 showed that they were monomeric in cyclohexane. Crystals of 1 and 4 were unsuitable for X-ray crystal structure determinations, but an X-ray data set for 6 showed that it was weakly dimerized in the solid with a long Ga-Ga bond of 2.6268(7) A and a trans-bent CGaGaC core array. The 1,2-diiodo-1,2-diaryldigallane compounds [Ga(Ar*)I](2) (2), [Ga(Ar#)I](2) (5), and [Ga(Ar')I](2) (7) were isolated as byproducts of the synthesis of 1, 4, and 6. The crystal structures of 2 and 7 showed that they had planar ICGaGaCI core arrays with Ga-Ga distances near 2.49 A, consistent with Ga-Ga single bonding. Treatment of 1, 4, and 6 with B(C(6)F(5))(3) immediately afforded the 1:1 donor-acceptor complexes ArGa[B(C(6)F(5))(3)] (Ar = Ar*, 8; Ar#, 9; Ar', 10) that featured almost linear gallium coordination, Ga-B distances near the sum of the covalent radii of gallium and boron, as well as some close Ga...F contacts. Compound 1 also reacted with Fe(CO)(5) under ambient conditions to give Ar*GaFe(CO)(4) (11), which had been previously synthesized by the reaction of GaAr*Cl(2) with Na(2)Fe(CO)(4). Reaction of 1 with 2,3-dimethyl-1,3-butadiene afforded the compound [Ar*GaCH(2)C(Me)C(Me)CH(2)]2 (12) that had a 10-membered 1,5-Ga(2)C(8) ring with no Ga-Ga interaction. Stirring 1 or 6 with sodium readily gave Na(2)[Ar*GaGaAr*] (13) and Na(2)(Ar'GaGaAr') (14). The former species 13 had been synthesized previously by reduction of GaAr*Cl(2) with sodium and was described as having a Ga-Ga triple bond because of the short Ga-Ga distance and the electronic relationship between [Ar*GaGaAr*](2-) and the corresponding neutral group 14 alkyne analogues. Compound 14 has a similar structure featuring a trans-bent CGaGaC core, bridged by sodiums which were also coordinated to the flanking aryl rings of the Ar' ligands. The Ga-Ga bond length was found to be 2.347(1) A, which is slightly (ca. 0.02 A) longer than that reported for 13. Reaction of Ga[N(Dipp)C(Me)](2)CH, 15 (i.e., GaN(wedge)NDipp(2)), which is sterically related to 1, 4, and 6, with Fe(CO)(5) yielded Dipp(2)N(wedge)NGaFe(CO)(4) (16), whose Ga-Fe bond is slightly longer than that observed in 11. Reaction of the less bulky LiAr"(Ar"= C(6)H(3)-2,6-Mes(2)) with "GaI" afforded the new paramagnetic cluster Ga(11)Ar(4)" (17). The ready dissociation of 1, 4, and 6 in solution, the long Ga-Ga distance in 6, and the chemistry of these compounds showed that the Ga-Ga bonds are significantly weaker than single bonds. The reduction of 1 and 6 with sodium to give 13 and 14 supplies two electrons to the di-gallium unit to generate a single bond (in addition to the weak interaction in the neutral precursor) with retention of the trans-bent geometry. It was concluded that the stability of 13 and 14 depends on the matching size of the sodium ion, and the presence of Na-Ga and Na-Ar interactions that stabilize their Na(2)Ga(2) core structures.

Reaction of Ar'MMAr' (M = Ga or In) with N3Ar' ' (Ar' = C6H3-2,6-Dipp2, Dipp = C6H3-2,6-Pri2, Ar' ' = C6H3-2,6(Xyl-4-But)2) afforded the first monomeric imides of heavier group 13 elements with two-coordinate metals. Planar, trans-bent structures with short M-N bond distances were observed, which are consistent with lone pair character at both M and N and a bond order less than the formally expected triple one.

Resistance to methyl-parathion among Nebraska western corn rootworm, Diabrotica virgifera virgifera LeConte, populations is associated with increased hydrolytic metabolism of an organophosphate insecticide substrate. An electrophoretic method to identify resistant individuals based on the staining intensity of esterase isozymes on nondenaturing polyacrylamide gels was developed. Three groups of esterases (I, II, and III) were visible on the gels, but only group II esterase isozymes were intensified in resistant populations. A total of 26 and 31 field populations of western corn rootworms from Nebraska (in 1998 and 1999, respectively) were assessed with nondenaturing polyacrylamide gel electrophoresis (PAGE) assays and diagnostic concentration bioassays. Significant correlations were observed between the two diagnostic assays. Group II esterase isozymes provide a reliable biochemical marker for detection of methyl-parathion resistance in individual western corn rootworms and a tool for monitoring the frequency of resistant individuals in field populations.

Treatment of M[N(SiMe(3))(2)](2) (M = Mn, Fe, Co) with various bulky beta-diketimines afforded a variety of new three-coordinate complexes which were characterized by UV-vis, (1)H NMR and IR spectroscopy, magnetic measurements, and X-ray crystallography. Reaction of the beta-diketimine H(Dipp)NC(Me)CHC(Me)N(Dipp) (Dipp(2)N(wedge)NH; Dipp = C(6)H(3)-2,6-Pr(i)(2)) with M[N(SiMe(3))(2)](2) (M = Mn or Co) gave Dipp(2)N(wedge)NMN(SiMe(3))(2) (M = Mn, 1; Co, 3) while the reaction of Fe[N(SiMe(3))(2)](2) with Ar(2)N(wedge)NH (Ar = Dipp, C(6)F(5), Mes, C(6)H(3)-2,6-Me(2), or C(6)H(3)-2,6-Cl(2)) afforded the series of iron complexes Ar(2)N(wedge)NFe[N(SiMe(3))(2)] (Ar = Dipp, 2a; C(6)F(5), 2b; Mes, 2c; C(6)H(3)-2,6-Me(2), 2d; C(6)H(3)-2,6-Cl(2), 2e). This represents a new synthetic route to beta-diketiminate complexes of these metals. The four-coordinate bis-beta-diketiminate complex Fe[N(wedge)N(C(6)F(5))(2)](2), 4, was also isolated as a byproduct from the synthesis of 2b. Direct reaction of the Dipp(2)N(wedge)NLi with CoCl(2) gave the "ate" salt Dipp(2)N(wedge)NCoCl(2)Li(THF)(2), 5, in which the lithium chloride has formed a complex with Dipp(2)N(wedge)NCoCl through chloride bridging. The Fe(III) species Dipp(2)N(wedge)NFeCl(2), 6, was obtained cleanly from the reaction of FeCl(3) with Dipp(2)N(wedge)NLi. Magnetic measurements showed that all the complexes have a high spin configuration. The different substituents in the series of iron complexes 2a-e allowed assignment of their paramagnetically shifted (1)H NMR spectra. The X-ray crystal structures 1-2d and 3 showed that they have a distorted three-coordinate planar configuration at the metals whereas complexes 4-6 have highly distorted four-coordinate geometries.

The synthesis and structure of a "diindene" with significant metal-metal bonding are described. It has an In-In distance of 2.9786(5) A, an In-In-C angle of 121.23(6) degrees , and an In-In bond order that is probably less than unity.

The reaction of Sn(Cl)C(6)H(3)-2,6-Dipp(2) (Dipp = C(6)H(3)-2,6-Pr(i)()(2)) with a stoichiometric amount of potassium in benzene affords 2,6-Pr(i)()(2)-H(3)C(6)SnSnC(6)H(3)-2,6-Pr(i)()(2) (1) as dark blue-green crystals. The compound 1 is a tin analogue of an alkyne. It was characterized by (1)H and (13)C NMR and UV-vis spectroscopy, cyclic voltammetry, combustion analysis and X-ray crystallography. The structural data show that 1 has a trans-bent, planar C(ipso)SnSnC(ipso) skeleton with a Sn-Sn bond distance of 2.6675(4) A and a Sn-Sn-C angle of 125.24(7) degrees. The Sn-Sn distance, which is ca. 0.15 A shorter than a conventional Sn-Sn single bond, and the trans-bent structure indicate the presence Sn-Sn multiple bond character unlike the related singly bonded ArPbPbAr species.