Synthèse du mèthyl-1 diformyl-2,3 pyrrole,de la méthyl-1 pyrrolo[2,3-d] pyridazine et de la méthyl-1 oxo-6 (6h)cycloheptatrieno[b] pyrrole

This communication describes the synthesis of l-methyl-2,3-diformylpyrrole. This new compound is used to prepare a new heterocycle, l-methylcyclohepta[b]pyrrol-6-one and thus allows a new synthesis of l-methylpyrrolo[2,3-d]pyridazine.     

Valence state and magnetic interactions in magnetically ordered Eu(Pd1−x Au x )2Si2

X-ray diffraction,¹⁵¹Eu Mössbauer effect (ME) and magnetic susceptibility measurements have been performed to investigate the valence behavior and the magnetic interactions of the Eu ions in the intermetallic series Eu(Pd_1–x Au _x )₂Si₂ (0x1) as a Forx>0.4 all experimental techniques are in agreement with each other and suggest a divalent 4f ⁷ ground state of the Eu ion. Belowx=0.4 the different methods lead to different results: while the lattice parameters and the ME isomer shift suggest an instable behavior of the valence the magnetic susceptibility proves a pure divalent 4f ⁷ ground state. These differences can be explained by assuming a partial extension of the 4f-shell radius such that the localized character of the 4f-electrons is preserved.Dedicated to B. Mühlschlegel on the occasion of his 60th birthday     

Crystal structures, electronic properties, and pressure-induced superconductivity of the tetrahedral cluster compounds GaNb(4)S(8), GaNb(4)Se(8), and GaTa(4)Se(8)

The crystal structures of the tetrahedral cluster compounds GaNb(4)S(8) and GaTa(4)Se(8) were determined by single-crystal X-ray diffraction. They crystallize in the cubic GaMo(4)S(8) structure type (F3m), which can be derived from the spinel type by shifting the metal atoms off the centers of the chalcogen octahedra along [111]. Electrical resistivity and magnetic susceptibility measurements show that the electronic conduction originates from hopping of localized unpaired electrons (S = (1)/(2)) among widely separated Nb(4) or Ta(4) clusters, and thus these materials represent a new class of Mott insulators. Under high pressure we find that GaNb(4)S(8) undergoes a transition from the Mott insulating to a superconducting state with T(C) up to 4 K at 23 GPa, similar to GaNb(4)Se(8) and GaTa(4)Se(8). High-pressure single-crystal X-ray studies of GaTa(4)Se(8) reveal that the superconducting transition is connected with a gradual decrease of the octahedral distortion with increasing pressure. DFT band structure calculations show that weakly coupled cluster orbitals are responsible for a high density of states at the Fermi level. The correct insulating magnetic ground state for GaNb(4)S(8) with mu(eff) = 1.73 mu(B) is for the first time achieved by the LDA+U method using U = 6 eV and rhombohedral symmetry.