Borane-amine adducts have received considerable attention, both as vectors for chemical hydrogen storage and as precursors for the synthesis of inorganic materials. Transition metal-catalyzed ammonia-borane (H3N-BH3, AB) dehydrocoupling offers, in principle, the possibility of large gravimetric hydrogen release at high rates and the formation of B-N polymers with well-defined microstructure. Several different homogeneous catalysts were reported in the literature. The current mechanistic picture implies that the release of aminoborane (e.g., Ni carbenes and Shvo's catalyst) results in formation of borazine and 2 equiv of H2, while 1 equiv of H2 and polyaminoborane are obtained with catalysts that also couple the dehydroproducts (e.g., Ir and Rh diphosphine and pincer catalysts). However, in comparison with the rapidly growing number of catalysts, the amount of experimental studies that deal with mechanistic details is still limited. Here, we present a comprehensive experimental and theoretical study about the mechanism of AB dehydrocoupling to polyaminoborane with ruthenium amine/amido catalysts, which exhibit particularly high activity. On the basis of kinetics, trapping experiments, polymer characterization by (11)B MQMAS solid-state NMR, spectroscopic experiments with model substrates, and density functional theory (DFT) calculations, we propose for the amine catalyst [Ru(H)2PMe3{HN(CH2CH2PtBu2)2}] two mechanistically connected catalytic cycles that account for both metal-mediated substrate dehydrogenation to aminoborane and catalyzed polymer enchainment by formal aminoborane insertion into a H-NH2BH3 bond. Kinetic results and polymer characterization also indicate that amido catalyst [Ru(H)PMe3{N(CH2CH2PtBu2)2}] does not undergo the same mechanism as was previously proposed in a theoretical study.

The iron complex [FeH­(CO) (PNP)] (PNP = N­(CH2CH2PiPr2)2) is a highly active catalyst for ammonia borane dehydrocoupling at room temperature. Mainly linear polyaminoborane is obtained upon release of 1 equiv of H2. Mechanistic studies suggest that both hydrogen release and B–N coupling are metal-catalyzed and proceed via free aminoborane. Catalyst deactivation results from reaction with free BH3 that is formed by aminoborane rearrangement. Importantly, borane trapping with a simple amine allows for the observation of a TON that is unprecedented for a well-defined base metal catalyst.

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Isotypic imidonitridophosphates MH4P6N12 (M = Mg, Ca) have been synthesized by high-pressure/high-temperature reactions at 8 GPa and 1000 °C starting from stoichiometric amounts of the respective alkaline-earth metal nitrides, P3N5, and amorphous HPN2. Both compounds form colorless transparent platelet crystals. The crystal structures have been solved and refined from single-crystal X-ray diffraction data. Rietveld refinement confirmed the accuracy of the structure determination. In order to quantify the amounts of H atoms in the respective compounds, quantitative solid-state (1)H NMR measurements were carried out. EDX spectroscopy confirmed the chemical compositions. FTIR spectra confirmed the presence of NH groups in both structures. The crystal structures reveal an unprecedented layered tetrahedral arrangement, built up from all-side vertex-sharing PN4 tetrahedra with condensed dreier and sechser rings. The resulting layers are separated by metal atoms.

The mechanisms by which amorphous intermediates transform into crystalline materials are still poorly understood. Here we attempt to illuminate the formation of an amorphous precursor by investigating the crystallization process of zinc phosphate hydrate. This work shows that amorphous zinc phosphate (AZP) nanoparticles precipitate from aqueous solutions prior to the crystalline hopeite phase at low concentrations and in the absence of additives at room temperature. AZP nanoparticles are thermally stable against crystallization even at 400 °C (resulting in a high temperature AZP), but they crystallize rapidly in the presence of water if the reaction is not interrupted. X-ray powder diffraction with high-energy synchrotron radiation, scanning and transmission electron microscopy, selected area electron diffraction, and small-angle X-ray scattering showed the particle size (≈20 nm) and confirmed the noncrystallinity of the nanoparticle intermediates. Energy dispersive X-ray, infrared, and Raman spectroscopy, inductively coupled plasma mass spectrometry, and optical emission spectrometry as well as thermal analysis were used for further compositional characterization of the as synthesized nanomaterial. (1)H solid-state NMR allowed the quantification of the hydrogen content, while an analysis of (31)P{(1)H} C rotational echo double resonance spectra permitted a dynamic and structural analysis of the crystallization pathway to hopeite.

In NMR, paramagnetic dopants change the relaxation behavior and the chemical shift of the nuclei in their immediate environment. Based on the concept that the "immediate environment" in a diamagnetic host material can be described as a sphere with radius r0, we developed a function for the fraction of unperturbed nuclei (the fraction of nuclei outside the sphere) which gives a link between the effective radius and the doping concentration. In the case of a homogeneous doping scenario a characteristic dependence is observed in both theory and experiment. We validated the model on a sample series where paramagnetic Eu(II) ions are doped into crystalline SrH2. The fraction of unperturbed nuclei was determined from the (1)H NMR signal and follows the predicted curve for a homogeneous doping scenario where the radius r0 is 17 Å.

A new synthesis route for phosphates in an organic solvent at low temperatures is presented. The synthesis was done by dispersing a nitrate salt and phosphorus pentoxide in dimethyl sulfoxide. The synthesis can be performed under water-free conditions and yielded several organic and inorganic phosphates. Crystal structure solution of bistetramethylammonium hydrogencyclotriphosphate, [N(CH3)4]2HP3O9, was achieved by combining information gained from powder X-ray diffraction, liquid NMR and solid state (2D) NMR. The molecular structure of rubidium cyclotetraphosphate, Rb4P4O12, was determined using liquid state NMR and solid state (2D) NMR spectroscopy.

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