Stearate-Coated Biogenic Calcium Carbonate from Waste Seashells: A Sustainable Plastic Filler.

Waste seashells from aquaculture are a massive source of biogenic calcium carbonate (bCC) that can be a potential substitute for ground calcium carbonate and precipitated calcium carbonate. These last materials find several applications in industry after a surface coating with hydrophobic molecules, with stearate as the most used. Here, we investigate for the first time the capability of aqueous stearate dispersions to coat bCC powders from seashells of market-relevant mollusc aquaculture species, namely the oyster Crassostrea gigas, the scallop Pecten jacobaeus, and the clam Chamelea gallina. The chemical-physical features of bCC were extensively characterized by different analytical techniques. The results of stearate adsorption experiments showed that the oyster shell powder, which is the bCC with a higher content of the organic matrix, showed the highest adsorption capability (about 23 wt % compared to 10 wt % of geogenic calcite). These results agree with the mechanism proposed in the literature in which stearate adsorption mainly involves the formation of calcium stearate micelles in the dispersion before the physical adsorption. The coated bCC from oyster shells was also tested as fillers in an ethylene vinyl acetate compound used for the preparation of shoe soles. The obtained compound showed better mechanical performance than the one prepared using ground calcium. In conclusion, we can state that bCC can replace ground and precipitated calcium carbonate and has a higher stearate adsorbing capability. Moreover, they represent an environmentally friendly and sustainable source of calcium carbonate that organisms produce by high biological control over composition, polymorphism, and crystal texture. These features can be exploited for applications in fields where calcium carbonate with selected features is required.

[Tl7]7- Clusters in Mixed Alkali Metal Thallides Cs7.29K5.71Tl13 and Cs3.45K3.55Tl7.

Investigations in the ternary system Cs-K-Tl resulted in the unexpected formation of new ternary thallides Cs7.29K5.71Tl13 and Cs3.45K3.55Tl7. Single crystal X-ray structure analyses of both compounds reveal the presence of isolated Tl cluster units. Cs7.29K5.71Tl13 crystallizes in the monoclinic space group C2/c (a = 30.7792(9) Å, b = 11.000(2) Å, c = 14.0291(4) Å, ß = 112.676(4)°, Z = 4) and contains [Tl6]6- and [Tl7]7- clusters as thallium subunits. Cs3.45K3.55Tl7 crystallizes in the tetragonal space group I41/a (a = 13.6177(2) Å, c = 25.5573(8) Å, Z = 8) and contains [Tl7]7- clusters exclusively. The formation of Cs7.29K5.71Tl13 is obtained after slow cooling in addition to that of Cs3.45K3.55Tl7 and can be suppressed by quenching the stoichiometric mixture. First dissolution experiments in liquid ammonia suggest thallium and amide as final oxidation products. Full relativistic band structure calculations of Cs4K3Tl7 and Cs8K5Tl13 showed a (pseudo) band gap around EF for both compounds.

A sustainable one-pot method to transform seashell waste calcium carbonate to osteoinductive hydroxyapatite micro-nanoparticles.

We have developed a straightforward, one-pot, low-temperature hydrothermal method to transform oyster shell waste particles (bCCP) from the species Crassostrea gigas (Mg-calcite, 5 wt% Mg) into hydroxyapatite (HA) micro/nanoparticles. The influence of the P reagents (H3PO4, KH2PO4, and K2HPO4), P/bCCP molar ratios (0.24, 0.6, and 0.96), digestion temperatures (25-200 °C), and digestion times (1 week-2 months) on the transformation process was thoroughly investigated. At 1 week, the minimum temperature to yield the full transformation significantly reduced from 160 °C to 120 °C when using K2HPO4 instead of KH2PO4 at a P/bCCP ratio of 0.6, and even to 80 °C at a P/bCCP ratio of 0.96. The transformation took place via a dissolution-reprecipitation mechanism driven by the favorable balance between HA precipitation and bCCP dissolution, due to the lower solubility product of HA than that of calcite at any of the tested temperatures. Both the bCCP and the derived HA particles were cytocompatible for MG-63 human osteosarcoma cells and m17.ASC murine mesenchymal stem cells, and additionally, they promoted the osteogenic differentiation of m17.ASC, especially the HA particles. Because of their physicochemical features and biological compatibility, both particles could be useful osteoinductive platforms for translational applications in bone tissue engineering.

Enhancing structural complexity: An experiment conducted in the Black Forest National Park, Germany.

We report on a structural complexity enhancement (SCE) experiment that was designed to test ecological restoration measures in the Black Forest National Park, Germany. The main goal was to understand as to whether the creation of standing and downed deadwood within previously managed, single-layered Norway spruce (Picea abies L.) forests accelerates the development of forest structure, richness, and diversity of a range of taxonomic groups. Here we introduce the experimental design and describe the development of stand structure including abundance and richness of tree-related microhabitats (TreMs) within 5 years after initiation of the experiment in October 2016. To enhance structural complexity in treatment plots, 10 trees per plot were toppled using a skidder winch, and another 10 trees were ring barked at a height of around 60 cm above ground level with a chainsaw. To monitor stand structure, we collected data on common forest attributes such as diameter at breast height (DBH), tree height, and TreMs of all trees in the six experimental and six control plots measuring 0.25 ha in size before the treatments were carried out in 2016 and again in 2020/21. We analyzed the abundance and richness of TreMs using generalized linear mixed models with DBH and treatment vs. control as predictors. The SCE treatment resulted in a significant increase in deadwood volumes (4.2 vs. 439.5 m3) as well as in TreM abundance and richness (increase of 0.74 TreMs per tree). This indicates that the SCE treatment was effective to increase biodiversity-relevant structures such as deadwood and TreMs, in previously managed Norway spruce-dominated stands. The ongoing monitoring of a range of taxonomic groups (birds, bats, small mammals, coleoptera, fungi, mosses, and vascular plants) in this experiment will demonstrate to what extent the enhancement in structural complexity will lead to an enrichment in species richness and diversity.

Recovering and Exploiting Aragonite and Calcite Single Crystals with Biologically Controlled Shapes from Mussel Shells.

Control over the shape and morphology of single crystals is a theme of great interest in fundamental science and for technological application. Many synthetic strategies to achieve this goal are inspired by biomineralization processes. Indeed, organisms are able to produce crystals with high fidelity in shape and morphology utilizing macromolecules that act as modifiers. An alternative strategy can be the recovery of crystals from biomineralization products, in this case, seashells. In particular, waste mussel shells from aquaculture are considered. They are mainly built up of single crystals of calcite fibers and aragonite tablets forming an outer and an inner layer, respectively. A simple mechanochemical treatment has been developed to separate and recover these two typologies of single crystals. The characterization of these single crystals showed peculiar properties with respect to the calcium carbonate from quarry or synthesis. We exploited these biomaterials in the water remediation field using them as substrate adsorbing dyes. We found that these substrates show a high capability of adsorption for anionic dye, such as Eosin Y, but a low capability of adsorption for cationic dyes, such as Blue Methylene. The adsorption was reversible at pH 5.6. This application represents just an example of the potential use of these biogenic single crystals. We also envision potential applications as reinforcing fillers and optical devices.

Turning Seashell Waste into Electrically Conductive Particles.

Biomaterials such as seashells are intriguing due to their remarkable properties, including their hierarchical structure from the nanometer to the micro- or even macroscopic scale. Transferring this nanostructure to generate nanostructured polymers can improve their electrical conductivity. Here, we present the synthesis of polypyrrole using waste seashell powder as a template to prepare a polypyrrole/CaCO3 composite material. Various synthesis parameters were optimized to produce a composite material with an electrical conductivity of 2.1 × 10-4 ± 3.2 × 10-5 S/cm. This work presents the transformation of waste seashells into sustainable, electronically conductive materials and their application as an antistatic agent in polymers. The requirements of an antistatic material were met for a safety shoe sole.

The Role of Different Alkali Metals in the A15Tl27 Type Structure and the Synthesis and X-ray Structure Analysis of a New Substitutional Variant Cs14.53Tl28.4.

Alkali metal thallides have been known since the report of E. Zintl on NaTl in 1932. Subsequently, binary and ternary thallides of alkali metals have been characterized. At an alkali metal proportion of approximately 33% (A:Tl~1:2, A = alkali metal), three different unique type structures are reported: K49Tl108, Rb17Tl41 and A15Tl27 (A = Rb, Cs). Whereas Rb17Tl41 and K49Tl108 feature a three-dimensional sublattice of Tl atoms, the A15Tl27 structure type includes isolated Tl11 clusters as well as two-dimensional Tl-layers. This unique arrangement is only known so far when the heavier alkali metals Rb and Cs are included. In our contribution, we present single-crystal X-ray structure analyses of new ternary and quaternary compounds of the A15Tl27 type structure, which include different amounts of potassium. The crystal structures allow for the discussion of the favored alkali metal for each of the four Wyckoff positions and clearly demonstrate alkali metal dependent site preferences. Thereby, the compound Cs2.27K12.73Tl27 unambiguously proves the possibility of a potassium-rich A15Tl27 phase, even though a small amount of cesium appears to be needed for the stabilization of the latter structure type. Furthermore, we also present two compounds that show an embedding of Tl instead of alkali metal into the two-dimensional substructure, being equivalent to the formal oxidation of the latter. Cs14.53Tl28.4 represents the binary compound with the so far largest proportion of incorporated Tl in the structure type A15Tl27.

Evaluating the effectiveness of retention forestry to enhance biodiversity in production forests of Central Europe using an interdisciplinary, multi-scale approach.

Retention forestry, which retains a portion of the original stand at the time of harvesting to maintain continuity of structural and compositional diversity, has been originally developed to mitigate the impacts of clear-cutting. Retention of habitat trees and deadwood has since become common practice also in continuous-cover forests of Central Europe. While the use of retention in these forests is plausible, the evidence base for its application is lacking, trade-offs have not been quantified, it is not clear what support it receives from forest owners and other stakeholders and how it is best integrated into forest management practices. The Research Training Group ConFoBi (Conservation of Forest Biodiversity in Multiple-use Landscapes of Central Europe) focusses on the effectiveness of retention forestry, combining ecological studies on forest biodiversity with social and economic studies of biodiversity conservation across multiple spatial scales. The aim of ConFoBi is to assess whether and how structural retention measures are appropriate for the conservation of forest biodiversity in uneven-aged and selectively harvested continuous-cover forests of temperate Europe. The study design is based on a pool of 135 plots (1 ha) distributed along gradients of forest connectivity and structure. The main objectives are (a) to investigate the effects of structural elements and landscape context on multiple taxa, including different trophic and functional groups, to evaluate the effectiveness of retention practices for biodiversity conservation; (b) to analyze how forest biodiversity conservation is perceived and practiced, and what costs and benefits it creates; and (c) to identify how biodiversity conservation can be effectively integrated in multi-functional forest management. ConFoBi will quantify retention levels required across the landscape, as well as the socio-economic prerequisites for their implementation by forest owners and managers. ConFoBi's research results will provide an evidence base for integrating biodiversity conservation into forest management in temperate forests.

Synthesis of the Tetragonal Phase of Zintl's NaTl and Its Structure Determination from Powder Diffraction Data.

A tetragonal distortion of the long-time known NaTl structure at 298 K was observed in different experimental setups, including Zintl's original procedure of reducing Tl(I)-iodide by sodium liquid ammonia solutions. The powder diffraction pattern obtained by the high temperature synthesis using classical solid-state techniques allowed a model-independent unambiguous structure solution and refinement of tetragonal distorted NaTl (Rp = 0.0179, wRp = 0.0246, R = 0.0477, wR = 0.0527, GooF = 1.24).

Stage-specific testes proteomics of Drosophila melanogaster identifies essential proteins for male fertility.

Spermiogenesis in Drosophila melanogaster is a highly conserved process and essential for male fertility. In this haploid phase of spermatogenesis, motile sperm are assembled from round cells, and flagella and needle-shaped nuclei with highly compacted genomes are formed. As transcription takes place mainly in spermatocytes and transcripts relevant for post-meiotic sperm development are translationally repressed for days, we comparatively analysed the proteome of larval testes (only germ cell stages before meiotic divisions), testes of 1-2-day-old pupae (germ cell stages before meiotic divisions, meiotic and early spermatid stages) and adult flies (germ cell stages before meiotic divisions, meiotic and early spermatid stages, late spermatids and sperm). We identified 6,171 proteins; 61 proteins were detected solely in one stage and are thus enriched, namely 34 in larval testes, 77 in pupal testes and 214 in adult testes. To substantiate our mass spectrometric data, we analysed the stage-specific synthesis and importance for male fertility of a number of uncharacterized proteins. For example, Mst84B (gene CG1988), a very basic cysteine- and lysine-rich nuclear protein and was present in the transition phase from a histone-based to a protamine-based chromatin structure. CG6332 encodes d-Theg, which is related to the mouse tHEG and human THEG proteins. Mutants of d-Theg were sterile due to the lack of sperm in the seminal vesicles. Our catalogue of proteins of the different stages of testis development in D. melanogaster will pave the road for future analyses of spermatogenesis.

Elusive Zintl Ions [µ-HSi4 ]3- and [Si5 ]2- in Liquid Ammonia: Protonation States, Sites, and Bonding Situation Evaluated by NMR and Theory.

The existence of [µ-HSi4 ]3- in liquid ammonia solutions is confirmed by 1 H and 29 Si NMR experiments. Both NMR and quantum chemical calculations reveal that the H atom bridges two Si atoms of the [Si4 ]4- cluster, contrary to the expectation that it is located at one vertex Si of the tetrahedron. The calculations also indicate that in the formation of [µ-HSi4 ]3- , protonation is driven by a high charge density and an increase of electron delocalization compared to [Si4 ]4- . Additionally, [Si5 ]2- was detected for the first time and characterized by NMR. Calculations show that it is resistant to protonation, owing to a strong charge delocalization, which is significantly reduced upon protonation. Thus, our methods reveal three silicides in liquid ammonia: unprotonated [Si5 ]2- , terminally protonated [HSi9 ]3- , and bridge-protonated [µ-HSi4 ]3- . The protonation trend can be roughly predicted by the difference in charge delocalization between the parent compound and the product, which can be finely tuned by the presence of counter ions in solution.

Nejire/dCBP-mediated histone H3 acetylation during spermatogenesis is essential for male fertility in Drosophila melanogaster.

Spermatogenesis in many species including Drosophila melanogaster is accompanied by major reorganisation of chromatin in post-meiotic stages, involving a nearly genome-wide displacement of histones by protamines, Mst77F and Protamine-like 99C. A proposed prerequisite for the histone-to-protamine transition is massive histone H4 hyper-acetylation prior to the switch. Here, we investigated the pattern of histone H3 lysine acetylation and general lysine crotonylation in D. melanogaster spermiogenesis to elucidate a possible role of these marks in chromatin reorganisation. Lysine crotonylation was strongest prior to remodelling and the deposition of this mark depended on the acetylation status of the spermatid chromatin. In contrast to H4 acetylation, individual H3 acetylation marks displayed surprisingly distinct patterns during the histone-to-protamine transition. We observed that Nejire, a histone acetyl transferase, is expressed during the time of histone-to-protamine transition. Nejire knock down led to strongly reduced fertility, which correlated with misshaped spermatid nuclei and a lack of mature sperm. protA and prtl99C transcript levels were reduced after knocking down Nejire. ProtB-eGFP, Mst77F-eGFP and Prtl99C-eGFP were synthesized at the late canoe stage, while histones were often not detectable. However, in some cysts histones persist in parallel to protamines. Therefore, we hypothesize that complete histone removal requires multiple histone modifications besides H3K18ac and H3K27ac. In summary, H3K18 and H3K27 acetylation during Drosophila spermatogenesis is dependent on Nejire or a yet uncharacterized acetyl transferase. We show that Nejire is required for male fertility since Nejire contributes to efficient transcription of protA and prtl99C, but not Mst77F, in spermatocytes, and to maturation of sperm.

The Structure of [HSi9 ]3- in the Solid State and Its Unexpected Highly Dynamic Behavior in Solution.

We report on the first unambiguous detection of the elusive [HSi9 ]3- anion in solutions of liquid ammonia by various 29 Si and 1 H NMR experiments including chemical exchange saturation transfer (CEST). The characteristic multiplicity patterns of both the 29 Si and 1 H resonances together with CEST and a partially reduced 1 H,29 Si coupling constant indicate the presence of a highly dynamic Si8 entity and a Si-H moiety with slow proton hopping. Theoretical calculations corroborate both reorganization of Si8 on the picosecond timescale via low vibrational modes and proton hopping. In addition, in a single-crystal X-ray study of (K(DB[18]crown-6))(K([2.2.2]crypt))2 [HSi9 ]⋅8.5 NH3 , the H atom was unequivocally localized at one vertex of the basal square of the monocapped square-antiprismatic cluster. Thus experimental studies and theoretical considerations provide unprecedented insight into both the structure and the dynamic behavior of these cluster anions, which hitherto had been considered to be rigid.

Promoting biodiversity values of small forest patches in agricultural landscapes: Ecological drivers and social demand.

Small forest patches embedded in agricultural (and peri-urban) landscapes in Western Europe play a key role for biodiversity conservation with a recognized capacity of delivering a wide suite of ecosystem services. Measures aimed to preserve these patches should be both socially desirable and ecologically effective. This study presents a joint ecologic and economic assessment conducted on small forest patches in Flanders (Belgium) and Picardie (N France). In each study region, two contrasted types of agricultural landscapes were selected. Open field (OF) and Bocage (B) landscapes are distinguished by the intensity of their usage and higher connectivity in the B landscapes. The social demand for enhancing biodiversity and forest structure diversity as well as for increasing the forest area at the expenses of agricultural land is estimated through an economic valuation survey. These results are compared with the outcomes of an ecological survey where the influence of structural features of the forest patches on the associated herbaceous diversity is assessed. The ecological and economic surveys show contrasting results; increasing tree species richness is ecologically more important for herbaceous diversity in the patch, but both tree species richness and herbaceous diversity obtain insignificant willingness to pay estimates. Furthermore, although respondents prefer the proposed changes to take place in the region where they live, we find out that social preferences and ecological effectiveness do differ between landscapes that represent different intensities of land use. Dwellers where the landscape is perceived as more "degraded" attach more value to diversity enhancement, suggesting a prioritization of initiatives in these area. In contrast, the ecological analyses show that prioritizing the protection and enhancement of the relatively better-off areas is more ecologically effective. Our study calls for a balance between ecological effectiveness and welfare benefits, suggesting that cost effectiveness studies should consider these approaches jointly.

Habitat properties are key drivers of Borrelia burgdorferi (s.l.) prevalence in Ixodes ricinus populations of deciduous forest fragments.

BACKGROUND: The tick Ixodes ricinus has considerable impact on the health of humans and other terrestrial animals because it transmits several tick-borne pathogens (TBPs) such as B. burgdorferi (sensu lato), which causes Lyme borreliosis (LB). Small forest patches of agricultural landscapes provide many ecosystem services and also the disservice of LB risk. Biotic interactions and environmental filtering shape tick host communities distinctively between specific regions of Europe, which makes evaluating the dilution effect hypothesis and its influence across various scales challenging. Latitude, macroclimate, landscape and habitat properties drive both hosts and ticks and are comparable metrics across Europe. Therefore, we instead assess these environmental drivers as indicators and determine their respective roles for the prevalence of B. burgdorferi in I. ricinus. METHODS: We sampled I. ricinus and measured environmental properties of macroclimate, landscape and habitat quality of forest patches in agricultural landscapes along a European macroclimatic gradient. We used linear mixed models to determine significant drivers and their relative importance for nymphal and adult B. burgdorferi prevalence. We suggest a new prevalence index, which is pool-size independent. RESULTS: During summer months, our prevalence index varied between 0 and 0.4 per forest patch, indicating a low to moderate disservice. Habitat properties exerted a fourfold larger influence on B. burgdorferi prevalence than macroclimate and landscape properties combined. Increasingly available ecotone habitat of focal forest patches diluted and edge density at landscape scale amplified B. burgdorferi prevalence. Indicators of habitat attractiveness for tick hosts (food resources and shelter) were the most important predictors within habitat patches. More diverse and abundant macro- and microhabitat had a diluting effect, as it presumably diversifies the niches for tick-hosts and decreases the probability of contact between ticks and their hosts and hence the transmission likelihood. CONCLUSIONS: Diluting effects of more diverse habitat patches would pose another reason to maintain or restore high biodiversity in forest patches of rural landscapes. We suggest classifying habitat patches by their regulating services as dilution and amplification habitat, which predominantly either decrease or increase B. burgdorferi prevalence at local and landscape scale and hence LB risk. Particular emphasis on promoting LB-diluting properties should be put on the management of those habitats that are frequently used by humans. In the light of these findings, climate change may be of little concern for LB risk at local scales, but this should be evaluated further.

Environmental drivers of Ixodes ricinus abundance in forest fragments of rural European landscapes.

BACKGROUND: The castor bean tick (Ixodes ricinus) transmits infectious diseases such as Lyme borreliosis, which constitutes an important ecosystem disservice. Despite many local studies, a comprehensive understanding of the key drivers of tick abundance at the continental scale is still lacking. We analyze a large set of environmental factors as potential drivers of I. ricinus abundance. Our multi-scale study was carried out in deciduous forest fragments dispersed within two contrasting rural landscapes of eight regions, along a macroclimatic gradient stretching from southern France to central Sweden and Estonia. We surveyed the abundance of I. ricinus, plant community composition, forest structure and soil properties and compiled data on landscape structure, macroclimate and habitat properties. We used linear mixed models to analyze patterns and derived the relative importance of the significant drivers. RESULTS: Many drivers had, on their own, either a moderate or small explanatory value for the abundance of I. ricinus, but combined they explained a substantial part of variation. This emphasizes the complex ecology of I. ricinus and the relevance of environmental factors for tick abundance. Macroclimate only explained a small fraction of variation, while properties of macro- and microhabitat, which buffer macroclimate, had a considerable impact on tick abundance. The amount of forest and the composition of the surrounding rural landscape were additionally important drivers of tick abundance. Functional (dispersules) and structural (density of tree and shrub layers) properties of the habitat patch played an important role. Various diversity metrics had only a small relative importance. Ontogenetic tick stages showed pronounced differences in their response. The abundance of nymphs and adults is explained by the preceding stage with a positive relationship, indicating a cumulative effect of drivers. CONCLUSIONS: Our findings suggest that the ecosystem disservices of tick-borne diseases, via the abundance of ticks, strongly depends on habitat properties and thus on how humans manage ecosystems from the scale of the microhabitat to the landscape. This study stresses the need to further evaluate the interaction between climate change and ecosystem management on I. ricinus abundance.

tBRD-1 and tBRD-2 regulate expression of genes necessary for spermatid differentiation.

Male germ cell differentiation proceeds to a large extent in the absence of active gene transcription. In Drosophila, hundreds of genes whose proteins are required during post-meiotic spermatid differentiation (spermiogenesis) are transcribed in primary spermatocytes. Transcription of these genes depends on the sequential action of the testis meiotic arrest complex (tMAC), Mediator complex, and testis-specific TFIID (tTFIID) complex. How the action of these protein complexes is coordinated and which other factors are involved in the regulation of transcription in spermatocytes is not well understood. Here, we show that the bromodomain proteins tBRD-1 and tBRD-2 regulate gene expression in primary spermatocytes and share a subset of target genes. The function of tBRD-1 was essential for the sub-cellular localization of endogenous tBRD-2 but dispensable for its protein stability. Our comparison of different microarray data sets showed that in primary spermatocytes, the expression of a defined number of genes depends on the function of the bromodomain proteins tBRD-1 and tBRD-2, the tMAC component Aly, the Mediator component Med22, and the tTAF Sa.

Dinuclear indium and thallium diyls: biscarbenoids or metal cluster?

Using bis(ß-diketiminate) ligands we were able to synthesize unprecedented indium and thallium biscarbenoids. For indium, a novel four-membered metallacycle is derived from intra- and intermolecular In-In interactions in the solid state, while for thallium only an intramolecular Tl2-pseudo-dimer is obtained. Computational studies revealed that the solid-state structures benefit significantly from dispersion stabilization.

Selective P4 Activation by a Highly Reduced Cobaltate: Synthesis of Dicobalt Tetraphosphido Complexes.

Although the chemistry of transition metal polyphosphide anions has attracted significant attention, there are few reports of studies in which such species have been synthesized directly from white phosphorus. [K(OEt2 )2 {Co(BIAN)(cod)}] (1, BIAN=1,2-bis(2,6-diisopropylphenylimino)acenaphthene, cod=1,5-cyclooctadiene), which is readily prepared by ligand exchange from [K(thf)x {Co(cod)2 }], reacts with P4 to afford [{K(thf)}2 {(BIAN)Co}2 (µ-η4 :η4 -P4 )] (2 a) in 61 % yield (isolated product). [{K(OEt2 )}2 {(BIAN)Co}2 (µ-η4 :η4 -P4 )] (2 b) and [K([18]crown-6)(MeCN)]2 [{(BIAN)Co}2 (µ-η4 :η4 -P4 )] (2 c) were obtained by recrystallizing 2 a from diethyl ether and acetonitrile (and using [18]crown-6 in case of 2 c). Oxidation of 2 a with [Cp2 Fe]BArF4 (one equivalent) and subsequent recrystallization of the product from different solvents gave [K(OEt2 ){(BIAN)Co}2 (µ-η4 :η4 -P4 )] (3 a) and [K(dme)4 ][{(BIAN)Co}2 (µ-η4 :η4 -P4 )] (3 b; dme=1,2-dimethoxyethane). Neutral [{(BIAN)Co}2 (µ-η4 :η4 -P4 )] (4) was obtained in moderate yield by oxidizing 2 a with two equivalents of [Cp2 Fe]BArF4 . The new complexes were characterized by NMR, EPR (in the case of 3 a), and UV/Vis spectroscopy, and elemental analysis. The molecular structures revealed by X-ray crystallography display planar cyclic or open-chain P44- units sandwiched between {(BIAN)Co} fragments.

Stability and Conversion of Tin Zintl Anions in Liquid Ammonia Investigated by NMR spectroscopy.

Homoatomic polyanions of post-transition main-group metals, namely, Zintl anions, are precast in analogous Zintl phases and can react in solution to form new materials. Despite comprehensible reaction approaches, the formed products cannot be planned in advance, as hitherto undetected and therefore disregarded side reactions take place. The outcomes and interpretations of the reactions of Zintl anions are so far based mainly on crystal structures, which only allow characterization of the product that has the lowest solubility. Here we present the results of our investigation of the stability of highly charged tin Zintl anions in liquid ammonia, which is not exclusively based on solution effects but also on the oxidative influence of the solvent. This allows for a deeper understanding of the ongoing processes in solution and opens doors to the directed synthesis of transition metal complexes of Sn4 (4-) , here shown by its reactivity towards MesCu.