Synthese und Struktur von MII[AuF4]2 (MII  Cd,Hg)

Synthesis and Structure of M^II[AuF₄]₂ (M^II ? Cd, Hg) Cd[AuF₄]₂ and the isotypic compound Hg[AuF₄]₂, both are yellow, crystallize tetragonal in the space-group P4/mcc-D (No. 124) with a = 575.0/575.6 pm, c = 1034.8/1042.3 pm and Z = 2. The single-crystals were obtained by solid-state reactions in goldtubes.     

[CrIII8MII6]12+ Coordination Cubes (MII=Cu, Co)

[Cr^III₈M^II₆]¹²⁺ (M^II=Cu, Co) coordination cubes were constructed from a simple [Cr^IIIL₃] metalloligand and a “naked” M^II salt. The flexibility in the design proffers the potential to tune the physical properties, as all the constituent parts of the cage can be changed without structural alteration. Computational techniques (known in theoretical nuclear physics as statistical spectroscopy) in tandem with EPR spectroscopy are used to interpret the magnetic behavior.     

Über K2PbO3 [1,2] Rb2PbO3 [3–5] und Cs2PbO3 [6,7]

On the Oxides A₂PbO₃ (A = K, Rb, Cs) The oxides A₂PbO₃ (A = K, Rb, Cs) have been reinvestigated [four-circle diffractometer PW 1100 (Fa. Philips), all particles ?anisotropically”? refined, parameters see text]. The structural features are confirmed, whereas the results on space group and parameters have to be partially corrected.     

Die Schwingungsspektren der Reihe [NPCl2]3 ċ [NCCl]3

Vibrational Spectra of the Series [NPCl₂]₃ ? [NCCl]₃ The vibrational spectra of the six-membered ring systems [NPCl₂]₂[NCCl] and [NPCl₂][NCCl]₂ are reported and discussed together with the spectra of [NPCl₂]₃ and [NCCl]₃.     

[3]Parycyclo− and [3]metacyclo[3](3,7)-p-tropoquinonophanes

The title phanes were synthesized. Examination of their physical properties including X-ray crystallography disclosed that 1) the p-tropoquinone ring is still bent in both compounds though to a lesser extent than in the corresponding [2.2]phanes, 2) the metacyclo compound prefers syn conformation in solution, and 3) the intramolecular CT interaction is very similar in two compounds.     

ChemInform Abstract: Ab initio Characterization of [H3N×BH3]2, [H3N×AlH3]2, and [H3N×GaH3]2.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

SeBr3[AlBr4] und TeI3[AlI4] – zwei weitere Vertreter des SCl3[AlCl4]-Strukturtyps

SeBr₃[AlBr₄] and TeI₃[AlI₄] – two further Compounds in the SCl₃[AlCl₄] Structure Type The reaction of SeBr₄ and AlBr₃ in a closed glass ampoule at 150°C yields quantitatively SeBr₃[AlBr₄] in form of yellow moisture sensitive crystals. From Te, two equivalents of I₂, and AlI₃ one obtains TeI₃[AlI₄] in form of dark red, moisture sensitive crystals. Both compounds crystallize monoclinic in the space group Pc (SeBr₃[AlBr₄]: a = 670.7(7) pm, b = 663.9(5) pm, c = 1 428.6(2) pm, β = 101.21(9)°, TeI₃[AlI₄]: a = 731.9(1) pm, b = 730.8(1) pm, c = 1 565.5(3) pm, β = 102.01(2)°). They are isotypic and have the SCl₃[AlCl₄] structure type. The structures are built of tetrahedral AlX₄^? ions and of pyramidal EX₃⁺ ions (E = S, Se, Te; X = Cl, Br, I). The chalcogen atoms are additionally coordinated by halogen atoms of surrounding AlX₄^? ions, corresponding to a strongly distorted octahedral coordination EX₃₊₃.     

Self－assembly of Novel Hetero[3]rotaxane, [2]Rotaxanes and [2]Catenane

One linear template 13 and one cyclophane template 15, both incorporating two electron rich 1,4‐dialkoxybenzene units and one diamide unit, have been synthesized. By utilizing donor‐acceptor interaction and/or intermolecular hydrogen bonding assembling principles, one novel hetero[3]rotazane 22·4Cl, possessing one neutral and one tetracationic ring components, has been synthesized from 13, through neutral [2]rotaxane 21 as intermediate. With 15 as template, tetracationic [2]catenane 23·4PF₆ was assembled by using donor‐acceptor interaction, but no neutral [2]rotaxane could be obtained under the typical conditions of hydrogen bonding assembling principle. The interlocked supramolecular compounds have been characterized and their spectral properties are investigated.     

Cs[Cl3F10]: A Propeller‐Shaped [Cl3F10]− Anion in a Peculiar A[5]B[5] Structure Type

Reaction of CsF with ClF₃ leads to Cs[Cl₃F₁₀]. It contains a molecular, propeller‐shaped [Cl₃F₁₀]^? anion with a central μ₃‐F atom and three T‐shaped ClF₃ molecules coordinated to it. This anion represents the first example of a heteropolyhalide anion of higher ClF₃ content than [ClF₄]^? and is the first Cl‐containing interhalogen species with a μ‐bridging F atom. The chemical bonds to the central μ₃‐F atom are highly ionic and quite weak as the bond lengths within the coordinating XF₃ units (X = Cl, and also calculated for Br, I) are almost unchanged in comparison to free XF₃ molecules. Cs[Cl₃F₁₀] crystallizes in a very rarely observed A^[5]B^[5] structure type, where cations and anions are each pseudohexagonally close packed, and reside, each with coordination number five, in the trigonal bipyramidal voids of the other.     

f‐Block Ansa Complexes in the Solid State: [3]Thoro‐ and [3]Uranocenophanes

The preparation of [3]thoro‐ and [3]uranocenophanes, the first structurally authenticated ansa‐bridged complexes of actinocenes, is reported. Following a flytrap route, 1,2‐bis(cyclooctatetraenyldimethylsilyl)methane was synthesized, reduced to its tetraanion, and subsequently converted into bridged uranocene and thorocene complexes by salt metathesis with the corresponding actinide tetrachlorides. In addition, their electronic structures have been investigated by experimental (UV/Vis spectroscopy, cyclic voltammetry) and theoretical (DFT) methods.     

Catalytic Divergent [3+3]‐ and [3+2]‐Cycloaddition by Discrimination Between Diazo Compounds

Highly selective divergent cycloaddition reactions of enoldiazo compounds and α‐diazocarboximides catalyzed by copper(I) or dirhodium(II) have been developed. With tetrakis(acetonitrile)copper(I) tetrafluoroborate as the catalyst epoxypyrrolo[1,2‐a]azepine derivatives were prepared in good yields and excellent diastereoselectivities through the first reported [3+3]‐cycloaddition of a carbonyl ylide. Use of Rh₂(pfb)₄ or Rh₂(esp)₂ directs the reactants to regioselective [3+2]‐cycloaddition generating cyclopenta[2,3]pyrrolo[2,1‐b]oxazoles with good yields and excellent diastereoselectivities.     

Cyanide-bridged tetradecanuclear RuII3MII11 clusters (MII=ZnII and CuII) based on the high connectivity building block [Ru3(HAT)(CN)12]6-: structural and photophysical properties

Reaction of the anionic cyanometallate chromophore [{Ru(CN)4}3(micro3-HAT)]6- with [MII(tren)]2+ complexes (M=ZnII, CuII) provides discrete tetradecanuclear clusters of formula [{MII(tren)(micro-CN)}11{Ru3(HAT)(CN)}]16+; the weak luminescence of the Ru3 chromophore is substantially enhanced in the presence of ZnII ions, whereas it is completely quenched when CuII centers are present.