Neue ternäre Phosphide und Arsenide des Caesiums mit Elementen der 8. Nebengruppe

New Ternary Phosphides and Arsenides of Cesium and Element of the 8th Transition Metal Group In the ternary systems Cesium/8^th transition metal group/5^th main group some new compounds were found and investigated. By single crystal measurements CsRh₂P₂ was found to crystallize in the space group 14/mmm with the lattice constants a = 390.11 pm and c = 1429.36 pm. The new compounds with the formula CsM₂X₂ (M = Fe, Co, Ru, Rh, Ir; X = P or As) crystallize in the ThCr₂Si₂-type structure, compounds of the formula Cs₂MX₂ (M = Ni, Pd, Pt; X = P or As) can be placed in a line with the K₂PdP₂-type structure.     

Synthesis, reaction and structure of a series of chromium(III) complexes containing oxalate ligand

A series of chromium(III) complexes [Cr(bipy)(HC₂O₄)₂]Cl·3H₂O (1), [Cr(phen)(HC₂O₄)₂]Cl·3H₂O (2), [Cr(phen)₂(C₂O₄)]ClO₄ (3), [Cr₂(bipy)₄(C₂O₄)](SO₄)·(bipy)_0.5·H₂O (4) and [Mn(phen)₂(H₂O)₂]₂[Cr(phen)(C₂O₄)₂]₃ClO₄·14H₂O (5) were synthesized (bipy=4,4′-bipyridine, phen=1,10-phenanthroline), while the crystal structures of 1 and 3–5 have been determined by X-ray analysis. 1 and 3 are mononuclear complexes, 4 contains binuclear chromium(III) ions and 5 is a 3D supromolecule formed by complicated hydrogen bonding. 1–3 are potential molecular bricks of chromium(III) building blocks for synthesis heterometallic complexes. When we use these molecular bricks as ligands to react with other metal salts, unexpected complexes 4 and 5 are isolated in water solution. The synthesis conditions and reaction results are also discussed.     

Synthesis, crystal structures and magnetic properties of Cu(II) compounds bridged by the terephthalate ligand and hydrogen bonds

A 3D network [Cu(tmen)(tp)(H₂O)₂]_n (1) (tmen = N,N,N′,N′-tetramethylethylenediamine; tp = terephthalate) and a 2D sheet [Cu(pyrazole)₂(tp)]_n (2), featuring 1D chains interwoven by hydrogen bonds, have been prepared and characterized by means of X-ray analyses and magnetic measurements. For 1, coordinative zigzag chains contain Cu(II) centers capped by the chelate ligand tmen, in which the tetragonal structure is elongated due to Jahn–Teller distortion. Coordinated water molecules are hydrogen-bonded to two free carboxylate oxygens of tp bridges, leading to the observed 3D structure. The use of the non-chelating capping ligand pyrazole produced the covalent-bonded 1D linear compound 2 with hydrogen bonds. A severe octahedral distortion of the Cu(II) center arises from a small bite angle (52.3(1)°) of two carboxylate oxygen atoms of tp, which are in turn hydrogen-bonded to the N–H groups of pyrazole ligands coordinated to Cu(II) atoms in neighboring chains. Magnetic data were fitted with the high-temperature series expansion for the Heisenberg chain spin Hamiltonian H = −J∑_iS_i · S_i + 1 together with consideration of the molecular field approximation (zJ′). Both compounds interestingly exhibit ferromagnetic interactions with g = 2.17, J = 4.08 cm⁻¹, zJ′ = −0.28 cm⁻¹ for 1 and g = 2.09, J = 1.47 cm⁻¹, zJ′ = −0.04 cm⁻¹ for 2. By taking into account structural parameters of distances between Cu atoms, it is reasonably assigned that the ferromagnetic couplings (J > 0) in these systems originate from the hydrogen bonds. The spin density of the d_x²-y² orbital on a Cu(II) atom in a chain is propagated and induced over the d_z² orbital of another Cu(II) atom in an adjacent chain. This orbital orthogonality gives rise to such interactions. The negative zJ′ term suggests that the tp bridges communicate only tiny antiferromagnetic interactions.     

Reaction between palladium(II) and gallium(III) halogenides in arenes: influence of halogen nature on the formation of binuclear palladium(I) clusters

Palladium(II) bromide reacts with gallium(III) bromide in the presence of arenes yielding binuclear palladium(I) complexes [Pd₂(GaBr₄)₂(arene)₂], where arene=benzene (1), toluene (2) and p-xylene (3). Reaction of palladium(II) chloride with gallium(III) chloride in p-xylene leads to the analogous palladium(I) compound [Pd₂(GaCl₄)₂(p-xylene)₂] (4); the X-ray structures of 1-4 were determined.     

Modular design of icosahedral metal clusters

The concept of crystalline module, that is, an unambiguously isolated, repeated quasi-molecular element, is introduced. This concept is more general than the concept of crystal lattice. The generalized modular approach allows extension of the methods and principles of crystallography to quasi-crystals, clusters, amorphous solids, and periodic biological structures. Principles of construction of aperiodic, nonequilibrium regular modular structures are formulated. Limitations on the size of icosahedral clusters are due to the presence of spherical shells with non-Euclidean tetrahedral tiling in their structure. A parametric relationship between the structures of icosahedral fullerenes and metal clusters of the Chini series was found.     

Synthesis of polyrotaxanes based on α-cyclodextrin and poly(ethylene oxide)

Inclusion complexes of poly(ethylene oxide) with α-cyclodextrin are the key compounds in the synthesis of polyrotaxanes. These complexes prepared in aqueous solutions contain free cyclodextrin, which cocrystallizes with the major reaction product. These complexes dissociate upon dissolution in DMF and DMSO to form cyclodextrin and pseudopolyrotaxanes with a low cyclodextrin content. Polyrotaxane was synthesized with the use of poly(ethylene oxide)-α,ω-bis-amine as a linear component. The end-groups of the polymer in the inclusion complex were modified by the reaction with 2,4-dinitrofluorobenzene. A procedure was developed for purification of a polyrotaxane with high cyclodextrin content. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1914–1918, August, 2005.     

Synthesis and molecular structure of 3-(2-aryl-2-oxoethyl)-3-methoxy-2-oxo-2,3-dihydroimidazo-[1,2-<Emphasis Type="Italic">a</Emphasis>]pyridine hydrochlorides

Reactions between 2-pyridylamides of Z-4-aryl-2-hydroxy-4-oxobut-2-enoic acids with diazomethane have been used to synthesize 3-(2-aryl-2-oxoethyl)-3-methoxy-2-oxo-2,3-dihydroimidazo[1,2-a]pyridines, which form hydrochlorides with hydrochloric acid. The structure of the latter has been demonstrated by XRD for the hydrochloride of 3-methoxy-2-oxo-3-(2-phenyl-2-oxoethyl)-2,3-dihydroimidazo[1,2-a]pyridine. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 464–468, 2007.     

Electrochemistry and complexation of Josiphos ligands

The oxidative electrochemistry of 11 chiral bis-phosphinoferrocene ligands, all within the Josiphos class of ligands, was examined in methylene chloride. The oxidation of these ligands displays multiple waves of varying chemical reversibility. Palladium(II) and platinum(II) complexes with the general formula [MCl₂(P-P)] (M = Pd or Pt; P-P = Josiphos) were prepared, characterized by NMR and cyclic voltammetry. The electrochemistry simplifies greatly upon coordination of the Josiphos ligands. The X-ray structures of a palladium(II) and platinum(II) complex of the same Josiphos ligand are reported.     

Chalkogenid-Disilicate der Lanthanoide vom Typ M4X3[Si2O7] (M  Ce?Er; X  S,Se)

M₄X₃[Si₂O₇]-Type Lanthanide Chalcogenide Disilicates (M ? Ce? Er; X ? S, Se) Attempts to produce single crystals of MSe₂ (or MSe^2?X) by vapour phase transport with iodine or the oxidation of MCl₂ (or MClH) with sulfur in the presence of NaCl in sealed evacuated quartz containers often yielded well-grown single crystals with the composition M₄X₃[Si₂O₇] (M ? pr, Sm, Gd, X ? Se, and M ? Nd, Er, X ? S) as by-products. The crystal structures (tetragonal, 14₁/amd (no. 141)), Z = 8, contain two crystallographically independent M₃₊ Cations that are interconnected by chalcogenide (X_2?) and disilicate anions ([Si₂O₇]^6?). (M1)³⁺ is surrounded by eight (five X^2? and three terminal O_2? of the disilicate group), (M2)³⁺ by nine (three X^2? and six terminal O^2? of the [Si₂O₇]_6? anion) chalcogenide anions. The disilicate anion itself exhibits the eclipsed conformation with non-linear Si? O? Si bridges (angles: 128 – 133°).     

(A19N7)[In4]2 (A = Ca,Sr) and (Ca4N)[In2]: Synthesis,Crystal Structures,Physical Properties,and Chemical Bonding

Single phase powders of (A₁₉N₇)[In₄]₂ (A = Ca, Sr) and (Ca₄N)[In₂] were prepared by reaction of melt beads of the metallic components with nitrogen. The crystal structure of (Ca₁₉N₇)[In₄]₂ was refined based on neutron and X‐ray powder diffraction data. The crystal structure of (Sr₁₉N₇)[In₄]₂ was solved from the X‐ray powder pattern. The structure refinements in combination with results from chemical analyses ascertain the compositions. The compounds (A₁₉N₇)[In₄]₂ (A = Ca, Sr) are isotypes of (Ca₁₉N₇)[Ag₄]₂; (Ca₁₉N₇)[In₄]₂ is probably identical to the earlier reported (Ca_18.5N₇)[In₄]₂. The crystal structure of the isotypes (A₁₉N₇)[In₄]₂ (A = Ca, Sr; cubic, , Ca: a = 1471.65(3) pm; Sr: a = 1561.0(1) pm) contains isolated [In₄] tetrahedra embedded in a framework of edge‐ and vertex‐sharing (A₆N) octahedra. Six of these octahedra are condensed by edge‐sharing around one central A²⁺ ion to form “superoctahedra” (A₁₉N₆) which are connected three‐dimensionally via further octahedra by corner‐sharing. The crystal structure of (Ca₄N)[In₂] (tetragonal, I4₁/amd, a = 491.14(4) pm, c = 2907.7(3) pm) consists of alternating layers of perovskite type slabs of vertex‐sharing octahedra (Ca₂Ca_4/2N) and parallel arranged infinite zigzag chains equation/tex2gif-stack-1.gif[In₂]. In the sense of Zintl‐type counting the compounds (A²⁺)₁₉(N^3?)₇[(In^2.125?)₄]₂ present an electron excess, (Ca²⁺)₄(N^3?)[(In^2.5?)₂] is electron deficient. Metallic properties are supported by electrical resistivity and magnetic susceptibility measurements. The analysis of the electronic structures gives evidence for the existence of homoatomic interactions In–In and significant heteroatomic metal–metal interactions Ca–In which favor the deviations of the title compounds from the (8 – N) rule.