Modular and Selective Arylation of Aryl Germanes (C−GeEt3) over C−Bpin,C−SiR3 and Halogens Enabled by Light-Activated Gold Catalysis

Selective C –C couplings are powerful strategies for the rapid and programmable construction of bi- or multiaryls. To this end, the next frontier of synthetic modularity will likely arise from harnessing the coupling space that is orthogonal to the powerful Pd-catalyzed coupling regime. This report details the realization of this concept and presents the fully selective arylation of aryl germanes (which are inert under Pd⁰/Pd^II catalysis) in the presence of the valuable functionalities C−BPin, C−SiMe₃, C−I, C−Br, C−Cl, which in turn offer versatile opportunities for diversification. The protocol makes use of visible light activation combined with gold catalysis, which facilitates the selective coupling of C−Ge with aryl diazonium salts. Contrary to previous light-/gold-catalyzed couplings of Ar–N₂⁺, which were specialized in Ar–N₂⁺ scope, we present conditions to efficiently couple electron-rich, electron-poor, heterocyclic and sterically hindered aryl diazonium salts. Our computational data suggest that while electron-poor Ar–N₂⁺ salts are readily activated by gold under blue-light irradiation, there is a competing dissociative deactivation pathway for excited electron-rich Ar–N₂⁺, which requires an alternative photo-redox approach to enable productive couplings.     

A Thioxanthone Sensitizer with a Chiral Phosphoric Acid Binding Site: Properties and Applications in Visible Light-Mediated Cycloadditions

A chiral phosphoric acid with a 2,2’-binaphthol core was prepared that displays two thioxanthone moieties at the 3,3’-position as light-harvesting antennas. Despite its relatively low triplet energy, the phosphoric acid was found to be an efficient catalyst for the enantioselective intermolecular [2+2] photocycloaddition of β-carboxyl-substituted cyclic enones (e.r. up to 93:7). Binding of the carboxylic acid to the sensitizer is suggested by NMR studies and by DFT calculations to occur by means of two hydrogen bonds. The binding event not only enables an enantioface differentiation but also modulates the triplet energy of the substrates.     

A HF Loaded Lewis-Acidic Aluminium Chlorofluoride for Hydrofluorination Reactions

The very strong Lewis acid aluminium chlorofluoride (ACF) was loaded with anhydrous HF. The interaction between the surface of the catalyst and HF was investigated using a variety of characterization methods, which revealed the formation of polyfluorides. Moreover, the reactivity of the HF-loaded ACF towards the hydrofluorination of alkynes was studied.     

Dialumenes – aryl vs. silyl stabilisation for small molecule activation and catalysis

Main group multiple bonds have proven their ability to act as transition metal mimics in the last few decades. However, catalytic application of these species is still in its infancy. Herein we report the second neutral NHC-stabilised dialumene species by use of a supporting aryl ligand (3). Different to the trans-planar silyl-substituted dialumene (3Si), compound 3 features a trans-bent and twisted geometry. The differences between the two dialumenes are explored computationally (using B3LYP-D3/6-311G(d)) as well as experimentally. A high influence of the ligand''s steric demand on the structural motif is revealed, giving rise to enhanced reactivity of 3 enabled by a higher flexibility in addition to different polarisation of the aluminium centres. As such, facile activation of dihydrogen is now achievable. The influence of ligand choice is further implicated in two different catalytic reactions; not only is the aryl-stabilised dialumene more catalytically active but the resulting product distributions also differ, thus indicating the likelihood of alternate mechanisms simply through a change of supporting ligand.

Ligand controlled reactivity: a trans-bent and twisted geometry enables dihydrogen activation and enhanced catalytic activity for NHC-stabilised dialumenes.     

Single-ion magnetism in the extended solid-state: insights from X-ray absorption and emission spectroscopy

Large single-ion magnetic anisotropy is observed in lithium nitride doped with iron. The iron sites are two-coordinate, putting iron doped lithium nitride amongst a growing number of two coordinate transition metal single-ion magnets (SIMs). Uniquely, the relaxation times to magnetisation reversal are over two orders of magnitude longer in iron doped lithium nitride than other 3d-metal SIMs, and comparable with high-performance lanthanide-based SIMs. To understand the origin of these enhanced magnetic properties a detailed characterisation of electronic structure is presented. Access to dopant electronic structure calls for atomic specific techniques, hence a combination of detailed single-crystal X-ray absorption and emission spectroscopies are applied. Together K-edge, L_2,3-edge and Kβ X-ray spectroscopies probe local geometry and electronic structure, identifying iron doped lithium nitride to be a prototype, solid-state SIM, clean of stoichiometric vacancies where Fe lattice sites are geometrically equivalent. Extended X-ray absorption fine structure and angular dependent single-crystal X-ray absorption near edge spectroscopy measurements determine Fe^I dopant ions to be linearly coordinated, occupying a D_6h symmetry pocket. The dopant engages in strong 3dπ-bonding, resulting in an exceptionally short Fe–N bond length (1.873(7) Å) and rigorous linearity. It is proposed that this structure protects dopant sites from Renner–Teller vibronic coupling and pseudo Jahn–Teller distortions, enhancing magnetic properties with respect to molecular-based linear complexes. The Fe ligand field is quantified by L_2,3-edge XAS from which the energy reduction of 3d_z² due to strong 4s mixing is deduced. Quantification of magnetic anisotropy barriers in low concentration dopant sites is inhibited by many established methods, including far-infrared and neutron scattering. We deduce variable temperature L₃-edge XAS can be applied to quantify the J = 7/2 magnetic anisotropy barrier, 34.80 meV (∼280 cm⁻¹), that corresponds with Orbach relaxation via the first excited, M_J = ±5/2 doublet. The results demonstrate that dopant sites within solid-state host lattices could offer a viable alternative to rare-earth bulk magnets and high-performance SIMs, where the host matrix can be tailored to impose high symmetry and control lattice induced relaxation effects.

Taking advantage of synchrotron light source methods, we present the geometric and electronic structure of iron doped in lithium nitride.     

Analysis of nitrophenols in cloud water with a miniaturized light-phase rotary perforator and HPLC-MS

An all-glass miniaturized light-phase rotary perforator for the enrichment of polar compounds has been modified/miniaturized and applied. Its application is demonstrated here for the analysis of nitrophenols and dinitrophenols from low-concentration/low-volume samples. For the method development of high-performance liquid chromatography–mass spectrometry (MS) four eluents were tested: (1) water–methanol, (2) acetic acid–methanol, (3) trifluoroacetic acid–methanol and (4) water–acetonitrile. The last eluent mentioned was used for the subsequent investigation of samples from field experiments. Detection limits varied between 1 ng and 50 pg. The relative standard deviation in repeated measurements was below 15%, corresponding to a good reproducibility. Recoveries ranged between 31 and 100%, showing a significant dependence on the extraction time and the final volume of the sample after evaporation. Quantification was carried out by using deuterated 4-nitrophenol and 2,4-dinitrophenol as standards and applying previously determined response factors. Structure determination of further substances under atmospheric pressure chemical ionization was performed by a first screening with a source collision-induced dissociation, followed by the definite analysis by MS ⁿ . The first results are shown for cloud water, fog water and rainwater samples from different locations.     

Self-assembly of supramolecular architectures and polymers by orthogonal metal complexation and hydrogen-bonding motifs

A modular construction kit with two orthogonal noncovalent binding sites for self-assembly of supramolecular architectures is presented. The heteroditopic building blocks contain a terpyridine (tpy) unit for coordination of metal ions and a Hamilton receptor for multiple H-bonding of cyanuric acid derivatives. The association constants of ligand binding of M(II) complexes (M=Ru, Zn, Fe, and Pt) with a dendritic end cap were determined to be in the range of 10(2) and 10(4) L mol(-1) in chloroform. The capabilities for binding of metal ions were investigated by (1)H NMR and UV/Vis spectroscopy. The Fe complexes are most appropriate for the generation of discrete and high-ordered architectures due to their strong tendency to form FeL(2) complexes. Superstructures are readily formed in a one-pot procedure at room temperature. No mutual interactions between the orthogonal binding motifs were observed, and this demonstrates the highly specific nature of each binding process. Decomplexation experiments were carried out to examine the reversibility of Fe-tpy coordination. Substitution of the terminal end cap with a homoditopic bis-cyanurate linkage leads to formation of an iron-containing supramolecular strand. Formation of coordination polymers was confirmed by viscosity measurements. The supramolecular polymer strands can be reversibly cleaved by addition of a terminating cyanuric acid building block, and this proves the dynamic nature of this noncovalent polymerization process.     

Synthesis and characterization of bis-cyclopropanated 1,3,5-tricarbonyl compounds. A combined synthetic, spectroscopic and theoretical study

Bis-cyclopropanated 1,3,5-tricarbonyl compounds were prepared by a sequence of Claisen condensations and cyclopropanations. The optimization of the conditions proved to be very important to suppress retro-Claisen reactions. The conformation of these molecules was studied by experimental and computational methods. The syn/syn;syn/syn conformation is present for all derivatives. It is exclusively present in the case of the derivative containing a phenyl group located at the terminal carbon atom. In most cases, equilibria with other conformers are found.