The chemistry of the p-block elements is a huge playground for fundamental and applied work.

Positive at last: The first condensed-phase homopolyatomic phosphorus cation [P(9)](+) was prepared using a combination of the oxidant [NO](+) and weakly coordinating anion, [Al{OC(CF(3))(3)}(4)](-). [P(9)](+) consists of two P(5) cages linked by a phosphonium atom to give a D(2d)-symmetric Zintl cluster. NMR (see picture), Raman, and IR spectroscopy, mass spectrometry, and quantum-chemical calculations confirmed the structure.

The layered compound Ni2P2S6 was electrochemically characterized for application as anode material in sodium-ion batteries (SIBs). A high reversible capacity of 621 mAh g 1 at 1 A g 1...

A series of gold acetonitrile complexes [Au(NCMe) ] [WCA] with weakly coordinating counterions (WCAs) was synthesized by the reaction of elemental gold and nitrosyl salts [NO] [WCA] in acetonitrile ([WCA] =[GaCl ] , [B(CF ) ] , [Al(OR ) ] ; R =C(CF ) ). In the crystal structures, the [Au(NCMe) ] units appeared as monomers, dimers, or chains. A clear correlation between the aurophilicity and the coordinating ability of counterions was observed, with more strongly coordinating WCAs leading to stronger aurophilic contacts (distances, C-N stretching frequencies of [Au(NCMe) ] units). An attempt to prepare [Au(L) ] units, even with less weakly basic solvents like CH Cl , led to decomposition of the [Al(OR ) ] anion and formation of [NO(CH Cl ) ] [F(Al(OR ) ) ] . All nitrosyl reagents [NO] [WCA] were generated according to an optimized procedure and were thoroughly characterized by Raman and NMR spectroscopy. Moreover, the to date unknown species [NO] [B(CF ) CN] was prepared. Its reaction with gold unexpectedly produced [Au(NCMe) ] [Au(NCB(CF ) ) ] , in which the cyanoborate counterion acts as an anionic ligand itself. Interestingly, the auroborate anion [Au(NCB(CF ) ) ] behaves as a weakly coordinating counterion, which becomes evident from the crystallographic data and the vibrational spectral characteristics of the [Au(NCMe) ] cation in this complex. Ligand exchange in the only room temperature stable salt of this series, [Au(NCMe) ] [Al(OR ) ] , is facile and, for example, [Au(PPh )(NCMe)] [Al(OR ) ] can be selectively generated. This reactivity opens the possibility to generate various [AuL L ] [Al(OR ) ] salts through consecutive ligand-exchange reactions that offer access to a huge variety of Au complexes for gold catalysis.

The Cu I salts [Cu(CH 3 CN) 4 ]PF and [Cu-(oDFB) 2 ]PF with the very weakly coordinating anion Al(OC(CF 3 ) 3 ) 4 À (PF) as well as [Cu(NEt 3 ) 2 ]PF comprising the unique, linear bis-triethylamine complex [Cu-(NEt 3 ) 2 ] + were synthesized and examined as catalysts for the conversion of monophenols to o-quinones. The activities of these Cu I salts towards monooxygenation of 2,4-di-tert-butylphenol (DTBP-H) were compared to those of [Cu(CH 3 CN) 4 ]X salts with "classic" anions (BF 4 À , OTf À , PF 6 À ), revealing an anion effect on the activity of the catalyst and a ligand effect on the reaction rate. The reaction is drastically accelerated by employing Cu II -semiquinone complexes as catalysts, indicating that formation of a Cu II complex precedes the actual catalytic cycle. This result and other experimental observations show that with these systems the oxygenation of monophenols does not follow a dinuclear, but a mononuclear pathway analogous to that of topaquinone cofactor biosynthesis in amine oxidase.

X-ray absorption spectroscopy investigations of the spin-state switching of spin-crossover (SCO) complexes adsorbed on a highly-oriented pyrolytic graphite (HOPG) surface have shown so far that HOPG is a promising candidate to realize applications such as spintronic devices because of the stability of SCO complexes on HOPG and the possibility of highly efficient thermal and light-induced spin-state switching. Herein, we present the spin switching of several Fe(II) SCO complexes adsorbed on an HOPG surface with particular emphasis on the thermally induced spin transition behaviour with respect to different structural modifications. The complexes of the type [Fe(bpz)2(L)] (bpz  =  dihydrobis(pyrazolyl)borate, L  =  1,10-phenanthroline, 2,2′-bipyridine) and their methylated derivatives exhibit SCO in the solid state with some differences regarding cooperative effects. However, in the vacuum-deposited thick films on quartz, complete and more gradual spin transition behavior is observable via UV/vis spectroscopy. In contrast to that, all complexes show large differences upon direct contact with HOPG. Whereas the unmodified complexes show thermal and light-induced SCO, the addition of e.g. two or four methyl groups leads to a partial or a complete loss of the SCO on the surface. The angle-dependent measurement of the N K-edge compared to calculations indicates that the complete SCO and HS-locked molecules on the surface exhibit a similar preferential orientation, whereas complexes undergoing an incomplete SCO exhibit a random orientation on the surface. These results are discussed in the light of molecule-substrate interactions.

With [Mo(N 2)(P 2 Me PP 2 Ph Scheme1.Molybdenum-based models ystems for synthetic nitrogen fixation.

The metallocene-based linker molecule 1,1′-ferrocenedicarboxylic acid (H2FcDC) was used to synthesize four different polymorphs of composition [In­(OH)­(FeC12H8O4)]. Using conventional solvent-based synthesis methods and varying the synthetic parameters such as metal source, reaction temperature, and solvent, two different MOFs and one 1D-coordination polymer denoted as CAU-43 (1), In-MIL-53-FcDC_a (2), and In-FcDC (3) were obtained. Furthermore, thermal treatment of CAU-43 (1) at 190 °C under vacuum yielded a new polymorph of 2, In-MIL-53-FcDC_b (4). Both MOFs 2 and 4 crystallize in a MIL-53 type structure, but in different space groups C2/m for 2 and P1̅ for 4. The structures of the four title compounds were determined by single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), or a combination of three-dimensional electron diffraction measurements (3D ED) and PXRD. N2 sorption experiments of 1, 2, and 4 showed specific surface areas of 355 m2 g–1, 110 m2 g–1, and 140 m2 g–1, respectively. Furthermore, the electronic properties of the title compounds were characterized via Mössbauer and EPR spectroscopy. All Mössbauer spectra showed the characteristic doublet, proving the persistence of the ferrocene moiety. In the cases of 1, 3, and 4, appreciable impurities of ferrocenium ions could be detected by electron paramagnetic resonance spectroscopy. Cyclovoltammetric experiments were performed to demonstrate the accessible redox activity of the linker molecule of the title compounds. A redox process of FcDC2– with oxidation (between 0.86 and 0.97 V) and reduction wave (between 0.69 and 0.80 V) was observed.