N-Heterocyclic Phosphenium Complex of Manganese: Synthesis and Catalytic Activity in Ammonia Borane Dehydrogenation.

A neutral N-heterocyclic phosphenium complex of manganese was synthesised by a metathesis approach and characterised by IR, NMR, and XRD studies. The short P-Mn distance suggests a substantial metal-ligand double bond character. Reaction with a hydride produced an anionic phosphine complex, which was also characterised by IR and NMR spectroscopy and, after anion exchange, a single-crystal XRD study. Protonation of the anion occurs at the metal to yield a neutral phosphine metal carbonyl hydride, which releases dihydrogen upon irradiation with UV light. These reactions confirm the electrophilic nature of the phosphenium ligand and suggest that the title complex might undergo reactions displaying metal-ligand cooperativity. Surprisingly, reaction with ammonia borane (AB) did not proceed under transfer hydrogenation of the Mn=P double bond but through the catalytic dehydrogenation of AB. The phosphenium complex behaves here as a class II catalyst, which dehydrogenates AB to NH2 BH2 that was trapped with cyclohexene. Computational model studies led to the identification of two possible catalytic cycles, which differ in the regioselectivity of the initial AB activation step. In one case, the activation proceeds as cooperative transfer hydrogenation of the Mn=P bond, whereas in the other case a H+ /H- pair is transferred to the phosphorus atom and a nitrogen atom of the phosphenium unit, resulting in a ligand-centred reaction in which the metal fragment acts merely as stabilising substituent. Unexpectedly, this pathway, which constitutes a new reaction mode for phosphenium complexes, seems to be better in accord with experimental findings on the course of the catalysis.

Variable Reactivity of a N-Heterocyclic Phosphenium Complex: P-C Bond Activation or "Abnormal" Deprotonation.

The reaction of an N-heterocyclic phosphenium complex of manganese with MeLi/Et3 NHCl under formal addition of CH4 to the Mn=P double bond can be reversed upon UV photolysis, providing a rare example for selective P-C(alkyl) bond activation. Action of LDA on the phosphenium complex does not proceed via attack at phosphorus but rather via C4-deprotonation to yield a unique P-analogue of an "abnormal" carbene. A transmetalation product of the original complex was fully characterized. The C-metalation is also applicable to bis-phosphenium complexes of other metals.

Systems knowledge for sustainable soil and land management.

While soils and land are pivotal elements of many Sustainable Development Goals (SDGs) and societal challenges, they face degradation and reduction of related functions and services worldwide. Societal demands on soils and land are increasing, including contributions to climate change mitigation and adaptation, ecosystem services, biodiversity and biomass production for food, feed, fiber and energy. This adverse combination of reducing capacities and increasing demands requires rapid transition towards sustainable soil and land management that mitigates trade-offs and creates synergies. Likewise, a transformation of soil and land research is required to scientifically support the sustainable transformation. Based on a literature analysis combined with engagement of soil and land scientists, we developed a systemic research framework for sustainable soil and land management to support the implementation of the Horizon Europe Mission "A Soil Deal for Europe". The framework summarizes soil and land related topics into six societal challenges and associates them with eight knowledge types that outline integrated research for development and implementation of sustainable soil and land management. We propose that research should be aligned with living labs and lighthouses to leverage local solutions, innovation, training and education. We outline the role of experimentation, data analysis, assessment, modelling and the importance of research for institutions, governance and policy support. For encouraging a swift transition towards a systems approach for sustainable soil and land management, we concluded that among all knowledge types, those addressing socio-economic interrelations with soil health and related policies currently represent the biggest bottleneck.

H+-Conducting Aromatic Multiblock Copolymer and Blend Membranes and Their Application in PEM Electrolysis.

As an alternative to common perfluorosulfonic acid-based polyelectrolytes, we present the synthesis and characterization of proton exchange membranes based on two different concepts: (i) Covalently bound multiblock-co-ionomers with a nanophase-separated structure exhibit tunable properties depending on hydrophilic and hydrophobic components' ratios. Here, the blocks were synthesized individually via step-growth polycondensation from either partially fluorinated or sulfonated aromatic monomers. (ii) Ionically crosslinked blend membranes of partially fluorinated polybenzimidazole and pyridine side-chain-modified polysulfones combine the hydrophilic component's high proton conductivities with high mechanical stability established by the hydrophobic components. In addition to the polymer synthesis, membrane preparation, and thorough characterization of the obtained materials, hydrogen permeability is determined using linear sweep voltammetry. Furthermore, initial in situ tests in a PEM electrolysis cell show promising cell performance, which can be increased by optimizing electrodes with regard to binders for the respective membrane material.

Suboxides with complex anions: the suboxoindate Cs9InO4.

Salty metal: In the suboxometallate Cs(9)InO(4), metallic cesium columns (see picture; blue) lie next to ionic oxoindate(III) columns. The chemistry of the suboxides is thus expanded to structures containing complex anions.

Defining habitat covariates in camera-trap based occupancy studies.

In species-habitat association studies, both the type and spatial scale of habitat covariates need to match the ecology of the focal species. We assessed the potential of high-resolution satellite imagery for generating habitat covariates using camera-trapping data from Sabah, Malaysian Borneo, within an occupancy framework. We tested the predictive power of covariates generated from satellite imagery at different resolutions and extents (focal patch sizes, 10-500 m around sample points) on estimates of occupancy patterns of six small to medium sized mammal species/species groups. High-resolution land cover information had considerably more model support for small, patchily distributed habitat features, whereas it had no advantage for large, homogeneous habitat features. A comparison of different focal patch sizes including remote sensing data and an in-situ measure showed that patches with a 50-m radius had most support for the target species. Thus, high-resolution satellite imagery proved to be particularly useful in heterogeneous landscapes, and can be used as a surrogate for certain in-situ measures, reducing field effort in logistically challenging environments. Additionally, remote sensed data provide more flexibility in defining appropriate spatial scales, which we show to impact estimates of wildlife-habitat associations.