Palladium‐Catalyzed Cross‐Coupling of Styrenes with Aryl Methyl Ketones in Ionic Liquids: Direct Access to Cyclopropanes

The combined use of Pd(OAc)₂, Cu(OAc)₂, and dioxygen in molten tetrabutylammonium acetate (TBAA) promotes an unusual cyclopropanation reaction between aryl methyl ketones and styrenes. The process is a dehydrogenative cyclizing coupling that involves a twofold C? H activation at the α‐position of the ketone. The substrate scope highlights the flexibility of the catalyst; a reaction mechanism is also proposed.     

A water- and sulfurization-free solution route to Cu2-xZn1+xSnS4

Zinc-rich/copper-poor Cu_2-xZn_1+xSnS₄ (x = 0.2, CZTS) has been successfully produced in film and powder form using two non-aqueous solutions (of metal salts and thiourea) without the need for sulfurization during the annealing phase. A reaction route is proposed and the choices of the solvents (water, ethyleneglycol, ethanol, methanol) and of the tin source (tin chloride pentahydrate or anhydrous) discussed and justified. A pure and coarse-grained material is obtained with a mix of metal salts in methanol and thiourea in ethylene glycol. The tin pentahydrate salt seems a better alternative to the commonly used anhydrous chloride.     

Light-Activated Rhenium Complexes with Dual Mode of Action against Bacteria

New antibiotics and innovative approaches to kill drug-resistant bacteria are urgently needed. Metal complexes offer access to alternative modes of action but have only sparingly been investigated in antibacterial drug discovery. We have developed a light-activated rhenium complex with activity against drug-resistant S. aureus and E. coli. The activity profile against mutant strains combined with assessments of cellular uptake and synergy suggest two distinct modes of action.     

Interplay of information quantifiers and the modified Jaynes-Cummings model

The dynamics of the Buck and Sukumar model (B. Buck and C. V. Sukumar, Phys. Lett. A 81, 132 (1981)) is investigated using different semi-classical information-theory tools. Their interplay reveals somewhat unexpected features. A new signature for the classical-quantum barrier is encountered thereby.     

Synthesis of side‐chain‐substituted ifosfamide analogs

Three analogs of the cytostatic drug ifosfamide incorporating 1‐methyl‐2‐chloroethyl side chains were designed and prepared as an attempt to obtain drugs of lower toxicity.     

One-dimensional polymers containing strictly collinear metal ions: synthesis and XRPD characterization of homoleptic binary metal pyrazolates

The synthesis of a number of 3d transition metal binary pyrazolates in microcrystalline form, thus suitable for a full XRPD characterization, has been pursued. The crystal and molecular structures of the Fe(pz)3, Co(pz)2, Co(pz)3, and Ni(pz)2 polymers, together with the few congeners reported in the recent literature, show that these species tend to afford highly crystalline materials where strictly collinear chains of metal atoms are present. Depending on the synthetic strategy used, Ni(pz)2 has been found to crystallize as two different alpha (orthorhombic) and beta (monoclinic) phases, possessing nearly identical intramolecular features. Data for each compound follow. Fe(pz)3: C9H9FeN6, hexagonal, P63/m, a = 9.1745(3) A, c = 7.2191(4) A, Z = 2. Co(pz)2: C6H6CoN4, orthorhombic, Ibam, a = 7.5239(5) A, b = 14.3461(9) A, c = 7.4331(5) A, Z = 4. Co(pz)3: C9H9CoN6, hexagonal, P63/m, a = 9.1966(3) A, c = 7.1051(3) A, Z = 2. Alpha-Ni(pz)2: C6H6N4Ni, orthorhombic, Cmcm, a = 16.6758(11) A, b = 6.4872(4) A, c = 6.9423(6) A, Z = 4. Beta-Ni(pz)2: C6H6N4Ni, monoclinic, P21/m, a = 9.967(2) A, b = 6.975(1) A, c = 6.016(1), A, beta = 98.50(1)degrees, Z = 2. The thermal stability and the detailed structural properties of these model compounds have been evaluated, in the light of the technologically relevant crystal phases (the well-known metal-diazolates showing reversible spin-crossover or spin-transition behavior) obtainable upon doping, magnetic dilution, and ring substitution (in the 4-position).