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 NH BH 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.

Phosphorus-containing multiple-bond systems have received great interest in various applications but often require elaborate syntheses and special precursors. In this paper, we describe simple methods for the synthesis of imidazoyl phosphinidenes and bis(imidazolyl)-P(I) halides from elemental phosphorus or the heptaphosphides Na 3 P 7 and (Me 3 Si) 3 P 7 . The reactions of imidazolium salts with KOtBu and P 4 afford mixtures of imidazoyl phosphinidenes and P n compounds and, for N-methylated imidazolium salts, also bis(imidazolyl)-P(I) hal- [a] Scheme 8. Transient intermediates E/Z-10 (R = mesityl) and 11 [40] observed during the reactions of imidazolium salt and /KOtBu with P 4 .

Symmetrical N‐heterocyclic 1,1′,3,3′‐tetrahydro‐2,2′‐bi‐1,3,2‐diazaphospholes and 2,2′‐bi‐1,3,2‐diazaphospholidines are prepared by time‐saving, sequential “one‐pot” syntheses starting from 1,4‐diazabutadienes or N‐alkyl or N‐aryl‐substituted ethane‐1,2‐diamines. This method offers high selectivity and minimizes the loss of products owing to unwanted hydrolysis, and thus grants high product yields. In some cases, secondary phosphanes were formed together with or instead of diphosphanes. This reaction is explained by a follow‐up process involving homolytic fission of diphosphanes to give phosphanyl radicals, which then react with ammonium salts to give a mixture of secondary phosphanes and chlorophosphanes. Even if its synthetic scope is as yet limited, this approach seems promising in offering superior selectivity and higher yields than common synthetic protocols that rely on the use of complex hydrides as reducing agents. In addition to the reductive conversion of diphosphanes into secondary phosphanes, a reverse reaction under exposure of the reactants to light is also reported.

The homolytic P-P bond fission in a series of sterically congested tetraaminodiphosphanes (R2N)2P-P(NR2)2 ({4}2-{9}2, two of which were newly synthesized and fully characterized) into diaminophosphanyl radicals (R2N)2P˙ (4-9) was monitored by VT EPR spectroscopy. Determination of the radical concentration from the EPR spectra permitted to calculate free dissociation energies ΔGDiss(295) as well as dissociation enthalpies ΔHDiss and entropies ΔSDiss, respectively. Large positive values of ΔGDiss(295) indicate that the degree of dissociation is in most cases low, and the concentration of persistent radicals--even if they are spectroscopically observable at ambient temperature--remains small. Appreciable dissociation was established only for the sterically highly congested acyclic derivative {9}2. Analysis of the trends in experimental data in connection with DFT studies indicate that radical formation is favoured by large entropy contributions and the energetic effect of structural relaxation (geometrical distortions and conformational changes in acyclic derivatives) in the radicals, and disfavoured by attractive dispersion forces. Comparison of the energetics of formation for CC-saturated N-heterocyclic diphosphanes and the 7π-radical 3c indicates that the effect of energetic stabilization by π-electron delocalization in the latter is visible, but stands back behind those of steric and entropic contributions. Evaluation of spectroscopic and computational data indicates that diaminophosphanyl radicals exhibit, in contrast to aminophosphenium cations, no strong energetic preference for a planar arrangement of the (R2N)2P unit.

Bipolar membrane|electrode interface water electrolyzers (BPEMWE) were found to outperform a proton exchange membrane (PEM) water electrolyzer reference in a similar membrane electrode assembly (MEA) design based on individual porous...

The interaction and nature of surface sites for water and methanol sorption on MFI-type zeolites and mesoporous SBA-15 were investigated by solid-state NMR spectroscopy and correlated with the desorption enthalpies determined via TGA/DSC. For siliceous Silicalite-1, 29Si CPMAS NMR studies support stronger methanol than water interactions with SiOH groups of Q3-type. On siliceous SBA-15, SiOH groups of Q2-type are accompanied by an enhanced hydrophilicity. In aluminum-containing Na-ZSM-5, Na+ cations are strong adsorption sites for water and methanol as evidenced by 23Na MAS NMR in agreement with high desorption enthalpies of ΔH = 66–74 kJ/mol. Solid-state NMR of aluminum-containing Na-[Al]SBA-15, in contrast, has shown negligible water and methanol interactions with sodium and aluminum. Desorption enthalpies of ΔH = 44–60 kJ/mol hint at adsorption sites consisting of SiOH groups influenced by distant framework aluminum. On H-ZSM-5, Brønsted acidic OH groups are strong adsorption sites as indicated by partial protonation of water and methanol causing low-field shifts of their 1H MAS NMR signals and enhanced desorption enthalpies. Due to the small number of Brønsted acid sites in aluminum-containing H-[Al]SBA-15, water and methanol adsorption on this material is suggested to mainly occur at SiOH groups with distant framework aluminum species, as in the case of Na-[Al]SBA-15.

The reaction of an N-heterocyclic phosphenium complex of manganese with MeLi/Et NHCl under formal addition of CH 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.

A lithio-diazaborole reacted with diamino-chlorophosphines via metathesis to yield previously unavailable phosphinoboranes bearing amino substituents at both the phosphorus and boron atoms, and with Ph2PCl and Mes*PCl2via chloride transfer and reductive PP coupling to give a chloro-diazaborole and the corresponding diphosphine or diphosphene, respectively. Diazaboroles with phenylphosphino- and PH2-substituents were nonetheless accessible via inverse metathesis upon treatment of a bromoborane precursor with phosphides PhnPH2-nM (n = 0-2, M = Li, K). The products were characterised by spectroscopic data and in most cases by single-crystal X-ray diffraction studies which show the molecules to exhibit strongly pyramidal coordination at the phosphorus atom and long BP bonds of 1.93-1.95 Å. The insensitivity of the BP distance towards substituent effects and the tolerance of large sterically induced torsional twists along the BP bond axis suggest the presence of pure single bonds without any contribution from P→B dative π-interactions. This view was confirmed by DFT studies which indicate further that the molecules lack a significant electrophilic character at boron but may act as potential σ-donor/π-acceptor ligands through the phosphorus atom.