Darstellung von trans-[Mo6Cl8]Cl4Br22−ausgehend von kristallisierten [Mo6Cl8]Cl4(H2O)2 und die Kristallstruktur von [(C6H5)4As]2[Mo6Cl8]Cl4Br2

Preparation of trans-[Mo₆Cl₈]Cl₄Br₂^2? Starting from Crystalline [Mo₆Cl₈]Cl₄(H₂O)₂ and Crystal Structure of [(C₆H₅)₄As]₂[Mo₆Cl₈]Cl₄Br₂ The synthesis of the title compound is successful if the crystallized [(Mo₆Cl₈)Cl₄(H₂O)₂] containing the H₂O molecules in trans-position reacts with HBr + [(C₆H₅)₄As]Br in ethanol in a heterogeneous reaction. The X-ray structure investigation confirms the existence of discrete trans-Br-substituted cluster anions of composition [(Mo₆Cl₈)Cl₄Br₂]^2? in the crystal. The reaction in homogeneous solutions proceeds to Br-enriched compounds. [(C₆H₅)₄As]₂[(Mo₆Cl₈)Cl₄Br₂] crystallizes in the triclinic space group P¯1 with a = 11.071(2), b = 11.418(2), c = 12.813(2) Å, α = 116.10(2), β = 95.27(2) and γ = 94.41(2)° (?133°C). The crystal structure at ?133°C was determined from single crystal X-ray diffraction data (R₁ = 0.026). The [(Mo₆Cl₈)Cl₄Br₂]^2?-anions are not completely ordered but distributed statistically among the three positions which are possible within the limits of the ordered [Mo₆Cl₈]-cores (ratio 11:5:4). The frameworks of the anions consist of Mo₆ cluster units with (slightly distorted) octahedral arrangement of the metal atoms (d(Mo? Mo): 2.600(1) up to 2.614(1) Å), which are coordinated by the halogeno ligands in a square-pyramidal manner. The details of the structure will be discussed and compared with similar [(Mo₆X₈)Y₄] cluster units (X, Y ? Cl, Br).     

Nine compounds containing high‐nuclearity [CunX2n+2]2− (n = 4, 5 or 7; X = Cl or Br) quasi‐planar oligomers

The structures of seven A₂Cu₄X₁₀ compounds containing quasi‐planar oligomers are reported: bis(1,2,4‐trimethylpyridinium) hexa‐μ‐chlorido‐tetrachloridotetracuprate(II), (C₈H₁₂N)₂[Cu₄Cl₁₀], (I), and the hexa‐μ‐bromido‐tetrabromidotetracuprate(II) salts of 1,2,4‐trimethylpyridinium, (C₈H₁₂N)₂[Cu₄Br₁₀], (II), 3,4‐dimethylpyridinium, (C₇H₁₀N)₂[Cu₄Br₁₀], (III), 2,3‐dimethylpyridinium, (C₇H₁₀N)₂[Cu₄Br₁₀], (IV), 1‐methylpyridinium, (C₆H₈N)₂[Cu₄Br₁₀], (V), trimethylphenylammonium, (C₉H₁₄N)₂[Cu₄Br₁₀], (VI), and 2,4‐dimethylpyridinium, (C₇H₁₀N)₂[Cu₄Br₁₀], (VII). The first four are isomorphous and contain stacks of tetracopper oligomers aggregated through semicoordinate Cu...X bond formation in a 4(,) stacking pattern. The 1‐methylpyridinium salt also contains oligomers stacked in a 4(,) pattern, but is isomorphous with the known chloride analog instead. The trimethylphenylammonium salt contains stacks of oligomers arranged in a 4(,) stacking pattern similar to the tetramethylphosphonium analog. These six structures feature inversion‐related organic cation pairs and hybrid oligomer/organic cation layers derived from the parent CuX₂ structure. The 2,4‐dimethylpyridinium salt is isomorphous with the known (2‐amino‐4‐methylpyridinium)₂Cu₄Cl₁₀ structure, in which isolated stacks of organic cations and of oligomers in a 4(,) pattern are found. In bis(3‐chloro‐1‐methylpyridinium) octa‐μ‐bromido‐tetrabromidopentacuprate(II), (C₆H₇ClN)[Cu₅Br₁₂], (VIII), containing the first reported fully halogenated quasi‐planar pentacopper oligomer, the oligomers stack in a 5(,) stacking pattern as the highest nuclearity [Cu_nX_2n+2]²⁻ oligomer compound known with isolated stacking. Bis(2‐chloro‐1‐methylpyridinium) dodeca‐μ‐bromido‐tetrabromidoheptacuprate(II), (C₆H₇ClN)₂[Cu₇Br₁₆], (IX), contains the second heptacopper oligomer reported and consists of layers of interleaved oligomer stacks with a 7[(,)][(−,−)] pattern isomorphous with that of the known 1,2‐dimethylpyridinium analog. All the oligomers reported here are inversion symmetric.     

Pursuing new facts in the coordination capabilities of (1-diaminomethylene)thiourea (HATU): Products of the interaction with transition metal halides – Structural investigations

This work is part of our studies on the reactivity and crystal engineering of (1-diaminomethylene)thiourea (HATU). Structure and other properties of the selected products of the interaction of HATU with transition metal halides, also in the presence of 3% hydrogen peroxide as an oxidizing agent, have been investigated ((1) di-μ-((1-diaminomethylene)thiouron-1-ium)-κ⁴S:S-bis[chlorido((1-diaminomethylene)-thiouron-1-ium-κS)copper(I)] tetrachloride [(C₂H₇N₄S)₄Cu^I₂Cl₂]Cl₄, (2) catena(bis(3,5-diamino-1,2,4-thiadiazol-2-ium)-bis(μ₂-chlorido)-chloridocuprate(II)) [(C₂H₆N₄S)₂(Cu₂Cl₆)]_∞, (3) 3,5-diamino-1,2,4-thiadiazol-2-ium pentachloridoferrate(III) (C₂H₆N₄S)₂[FeCl₅], (4) 3,5-diamino-1,2,4-thiadiazol-2-ium chloride) (C₂H₆N₄S)Cl, (5) 3,5-diamino-1,2,4-thiadiazol-2-ium tetrachloridozincate(II) (C₂H₇N₄S)₂[ZnCl₄]. For (2) also magnetic properties have been characterized. Compound (3) contains unusual pentachloridoferrate(III) anions.     

The correct formulation of the sulfur transfer reagent benzyltriethylammonium tetracosathioheptamolybdate

The recently reported sulfur transfer reagent benzyltriethylammonium tetracosathioheptamolybdate [(PhCH₂)N(C₂H₅)₃]₆[Mo₇S₂₄] [Tetrahedron Lett. 2003, 44, 887] is correctly formulated as benzyltriethylammonium tetrathiomolybdate [(PhCH₂)N(C₂H₅)₃]₂[MoS₄]. The correct formulation explains the unusual sulfur transfer properties of [(PhCH₂)N(C₂H₅)₃]₆[Mo₇S₂₄] observed in the earlier work.     

Synthesis and Structures of Silver(I) and Copper(I) 3,5-Dipentyl-1,2,4-Triazolates

The Ag(I) and Cu(I) complexes of 4-amino-3,5-dipentyl-4H-1,2,4-triazole (4-NH₂-3,5-(C₅H₁₁)₂tz) and 3,5-dipentyl-1H-1,2,4-triazole (3,5-(C₅H₁₁)₂tzH) have been synthesized and characterized. X-Ray analysis shows that {Ag₄[4-NH₂-3,5-(C₅H₁₁)₂tz]₆}(BF₄)₄ is a tetranuclear complex featuring an Ag₄tz₆ cluster; {Ag[3,5-(C₅H₁₁)₂tz]}_n exhibits a 3D structure of lvt-a topology; and {Cu₂[3,5-(C₅H₁₁)₂tz]Br}_n is a Cu₄Br₄-cluster based 3D complex with the dia topology.     

Bis(tetramethylammonium) hexaaquadodeca‐μ‐bromo‐octahedro‐hexatantalum tetrabromide dihydrate

The novel title compound, [(CH₃)₄N]₂[Ta₆Br₁₂(H₂O)₆]Br₄·2H₂O, with a [Ta₆Br₁₂]²⁺ cluster unit, has been prepared and structurally characterized. The compound crystallizes in space group C2/c, with a twofold axis passing through the cluster and the centre of symmetry located between the clusters. The nearest neighbouring cluster units are aligned along the crystallographic c axis, forming a one‐dimensional chain pattern.     

SYNTHESIS AND CHARACTERIZATION OF TWO NOVEL,NEST-SHAPED Mo-Cu-S CLUSTER COMPOUNDS, [MoOS3Cu3(Py)5X] (X = Br,I), AND THE SUBSTITUTION OF Mo-Cu-S CLUSTERS

Abstract

The title compounds [MoOS₃Cu₃(Py)₅Br] (3) and [MoOS₃Cu₃(Py)₅I] (4) were obtained through the nest-shaped cluster [(n-Bu)₄N]₂[MoOS₃Cu₃BrCl₂] (1) and twin-nest-shaped cluster [Et₄N]₄[Mo₂Cu₆S₆O₂Br₂I₄](2) by reacting with pyridine. They show nest-shaped skeletons, and are characterized structurally by single-crystal X-ray analysis. These are the first neutral nest-shaped Mo(W)-Cu(Ag)-S clusters.     

Structural and spectroscopic characterization of the dirhenium acetamidate products resulting from the hydrolysis of acetonitrile

Unsaturated molecules such as nitriles are activated upon coordination to a dirhenium core. Acetonitrile is hydrolyzed in the presence of water to produce coordinated bridging acetamidate ligands as demonstrated by the reaction of [N(C₄H₉)₄]₂[Re₂Cl₈] with CH₃CN and water in ethanol to form the acetamidate complexes, [N(C₄H₉)₄][Re₂Cl₅(μ-CH₃C(O)NH)(μ-CH₃C(OH)N)]·3CH₂Cl₂ [I] and Re₂Cl₄(μ-CH₃C(O)NH)(μ-dppm)₂·4 CH₂Cl₂/0.833 EtOH [II]. Compound II is formed when I is reduced upon coordination of bis(diphenylphosphino)methane (dppm). Compounds I and II were characterized using X-ray crystallography and a variety of other spectroscopic methods.     

Influence of Cl/Br substitution on the stereochemical peculiarities of copper(I) π‐complexes with the 1‐allyl‐2‐amino­pyridinium cation

By using alternating‐current electrochemical synthesis, crystals of the Cu^Iπ‐complexes bis(1‐allyl‐2‐amino­pyridinium) di‐μ‐chloro‐bis­[chloro­copper(I)], (C₈H₁₁N₂)₂[Cu₂Cl₄] or [H₂NC₅H₄NC₃H₅][CuCl₂], and bis(1‐allyl‐2‐amino­pyridinium) di‐μ‐(chloro/bromo)‐bis­[(chloro/bromo)copper(I)], (C₈H₁₁N₂)₂[Cu₂Br_2.2Cl_1.8] or [H₂NC₅H₄NC₃H₅][CuBr_1.10Cl_0.90], have been obtained and structurally investigated. In each of the isostructural (isomorphous) compounds, the distorted tetrahedral Cu environment involves three halide atoms and the C=C bond of the ligand. Both compounds reside on inversion centres, and the dimeric [Cu₂X₄·2H₂NC₅H₄NC₃H₅] units are bonded into a three‐dimensional structure by N—H⋯X hydrogen bonds. The Br content in the terminal X1 position is much higher than that in the bridged X2 site.     

Darstellung,Redox-Verhalten und Strukturen einkerniger „einfacher”︁ Mono- und Dinitrosyl-Komplexe des Molybdäns mit Hydroxylamido(−1)-, Oximato-, Halogeno- und Pseudohalogeno-Liganden

Preparation, Redox Properties, and Structures of Mononuclear ?Simple”? Mono-, and Dinitrosyl Complexes of Molybdenum with Hydroxylamido(?1), Oximato, Halogeno, and Pseudohalogeno Ligands The compounds [(C₆H₅)₄P]₂[Mo(NO)(H₂NO)(NCS)₄] 1 , [(C₆H₅)₄P]₂ [Mo(NO)((C₂H₅)₂-CNO)(NCS)₄] 2 , [(C₆H₅)₄P]₂[Mo(NO)₂(NCS)₄] · CH₃OH, 3 [(C₆H₅)₄P]₃[Mo(NO)(CN)₅] · 2H₂O 4 , Cs₂[Mo(NO)Cl₄(H₂O)] 5 and Cs₂[Mo(NO)Cl₅] 6 were prepared and characterized by complete X-ray structure analysis. All complexes have a nearly linear MoNO moiety, whereas in the anions of 1 and 2 a pentagonal-bipyramidal, in 3 — 6 an octahedral coordination sphere of Mo is present. Complexes with {MoNO}ⁿ configuration (n = 4, 5, 6) can be converted into each other by remarkable redox-reactions. Some novel reactions of the hydroxylamido(?1)-ligand (formation of 2 and 3 ) are discussed very shortly.     

Determination of kinetic parameters of inorganic metalporphyrins

The thermal properties of four heteropoly complexes α-K₃H₃[SiW₁₁Ni(H₂O)O₃₉]·11.5H₂O (I), α-K₃H₂[SiW₁₁Fe(H₂O)O₃₉]·9H₂O (II), α-[(C₄H₉)₄N]_3.5H_1.5[SiW₁₁Fe(H₂O)O₃₉]·4.5H₂O (III) and α-[(C₄H₉)₄N]_3.5H_2.5[SiW₁₁Cu(H₂O)O₃₉]·6H₂O (IV) were studied by means of TG, DTA and DSC. The activation energy and reaction order of the thermal decomposition reaction of these complexes have been calculated.

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Zusammenfassung Mittels TG, DTA und DSC wurden die thermischen Eigenschaften der vier heteropolaren Komplexe α-K₃H₃[SiW₁₁Ni(H₂O)O₃₉]·11.5H₂O (I), α-K₃H₂[SiW₁₁Fe(H₂O)O₃₉]·9H₂O (II), α-[(C₄H₉)₄N]_3.5H_1,5[SiW₁₁Fe(H₂O)O₃₉]·4.5H₂O (III) und α-[(C₄H₉)₄N]_3.5H_2,5 [SiW₁₁Cu(H₂O)O₃₉]·6H₂O (IV) untersucht. Die Aktivierungsenergie und Reaktionsordnung der thermischen Zersetzungsreaktion dieser Komplexe wurde berechnet.

     

Polynuclear clusters of technetium. I. Synthesis,crystal and molecular structure of bromide octanuclear lrismatic and hexanuclear octahedral clusters of technetium

The synthesis, crystal and molecular structure of the first representatives of polynuclear technetium clusters are described. The composition of these clusters is: [Tc₈Br₄μ? Br₈]Br. 2H₂O; [H(H₂O)₂][Tc₈Br₄μ? Br₈]Br; [H(H₂O)₂]₂[Tc₈Br₄μ? Br₈]Br₂; [H₃O(H₂O)₃]₂[Tc₆Br₆μ₃? Br₅]; [(C₄H₉)₄N]₂[Tc₆Br₆μ₃? Br₅]; [H₃O₃]₂[Tc₆Br₆μ₃? Br₅]. 4 H₂O. It is shown that these clusters strongly differ in their structure from the known clusters of other d-elements. The crystal and molecular structure of hexabromotechetium acid (H₃O)₂TcBr₆ is studied too.     

Tetrakis­(tetra­methyl­ammonium) dodeca‐μ‐chloro‐hexa­chloro‐octahedro‐hexatantalate chloride

The title compound, (C₄H₁₂N)₄[Ta₆Cl₁₈]Cl, crystallizes in the cubic space group . The crystal structure contains two different types of coordination polyhedra, i.e. four tetrahedral [(CH₃)₄N]⁺ cations and one octahedral [(Ta₆Cl₁₂)Cl₆]³⁻ cluster anion, and one Cl⁻ ion. The presence of three different kinds of Cl atoms [bridging (μ₂), terminal and counter‐anion] in one mol­ecule makes this substance unique in the chemistry of hexanuclear halide clusters of niobium and tantalum. The Ta₆ octahedron has an ideal O_h symmetry, with a Ta—Ta interatomic distance of 2.9215 (7) Å.     

Unusual electrochemical reduction of copper(II) to copper(I) in polyoxotungstates

The electrochemical behaviour of the copper-substituted Keggin-type and sandwich-type polyoxotungstate anions of the compounds α-[(C₄H₉)₄N]₄H[PW₁₁Cu^IIO₃₉] and α-B-[(C₄H₉)₄N]₇H₃[Cu^II₄(H₂O)₂(PW₉O₃₄)₂] was studied by cyclic voltammetry in acetonitrile. In both cases two copper 1-electron reduction waves were detected in the cathodic scan. The first one was due to the reduction of one Cu^II to Cu^I in the polyoxoanion and the second one to the consecutive reduction of the preformed Cu^I to Cu⁰, with the consequent deposition/adsorption of the ejected metal atom at the glassy carbon electrode surface. In the anodic scan, Cu⁰ was re-oxidised with regeneration of the initial copper(II) complexes, via a Cu^I intermediate. The observed two-step reduction of copper(II) to copper(0) and the formation of intermediate species containing copper(I) is here reported for the first time for copper substituted polyoxotungstates. The co-ordination of the acetonitrile molecules to the copper ions must play a role in the formation of the copper(I) species, which are not detected in aqueous solution.     

Complexation of N-Allyl Derivatives of Morpholinium with Copper(I) Halides: Synthesis and Crystal Structure of [C4H8ON(C3H5)2]+[Cu4Cl5]–, [C4H8ONH(C3H5)]+[CuBr2]–, and [C4H8ONH(C3H5)]+[CuBr1.41Cl0.59]–

The compounds [C₄H₈ON(C₃H₅)₂]⁺[Cu₄Cl₅]^– (I), [C₄H₈ONH(C₃H₅)]⁺[CuBr₂]^– (II), and [C₄H₈ONH(C₃H₅)]⁺[CuBr_1.41Cl_0.59]^– (III) were prepared for the first time by ac electrochemical synthesis from mono- and di-N-allyl derivatives of morpholinium and copper(I) halides in ethanol solution and structurally characterized. In the structure of I π-complex, the centrosymmetric Cu₈Cl₁₀ fragments are associated into layers perpendicular to the b axis. The N,N"-diallylmorpholinium cation functions as a bridge, which coordinates two copper atom of the adjacent inorganic fragments by both allyl groups. The trigonal-pyramidal surrounding of the Cu(I) atom, as well as the distorted tetrahedral coordination sphere of Cu(2), involves three chlorine atoms and the C=C bond, whereas the planar trigonal surrounding of the Cu(3) atom and trigonal-pyramidal surrounding of the Cu(4) atom involve only chlorine atoms. In the isostructural II and III σ-complexes, the edge-shared CuX₄ tetrahedra form the infinite copper-halide chains running along the a axis. The inorganic fragments and organic N-allylmorpholinium cations are united into the three-dimensional crystal structures by N–H···X and C–H···X (X = Cl, Br) hydrogen bonds.     

The closo-Cluster Triad: B9X9, [B9X9]· –, and [B9X9]2– with Tricapped Trigonal Prisms (X = Cl,Br, I). Syntheses,Crystal and Electronic Structures

Halogenation of nido-B₁₀H₁₄ with C₂H₂Cl₄, C₂Cl₆, Br₂, or I₂, produces by cluster degradation the (2 n)-closo-clusters B₉X₉ (X = Cl, Br, I). The synthesis of salts of the perhalogenated radical anions of the type (2 n + 1)-closo-[B₉X₉]^{· –} and of the corresponding dianions (2 n + 2)-closo-[B₉X₉]^2– from neutral B₉X₉ is described [n is the number of cluster atoms; (2 n), (2 n + 1), and (2 n + 2) is the number of cluster electrons]. Molecular and crystal structures of B₉Cl₉, B₉Br₉, [(C₆H₅)₄P][B₉Br₉] · CH₂Cl₂, and [(C₄H₉)₄N]₂[B₉Br₉] · CH₂Cl₂ have been determined via X-ray diffraction. All three oxidation states of the cluster retain the tricapped trigonal prism. The reduction of the clusters B₉X₉ was shown by cyclic voltammetry in CH₂Cl₂ to proceed via two successive one-electron reversible steps, separated by at least 0.4 V. The paramagnetic radical anions [B₉X₉]^{· –} (X = Cl, Br) were further characterized by magnetic susceptibility measurements of [Cp₂Fe][B₉X₉] and [Cp₂Co][B₉X₉], respectively. The EPR spectra of [B₉X₉]^{· –} (X = Cl, Br, I) in glassy frozen CH₂Cl₂ solutions showed increasing g anisotropy for the heavier halogen derivatives, illustrating significant halogen participation at the singly occupied MO. The ¹¹B NMR spectra of CD₂Cl₂ solutions of the neutral clusters B₉X₉ exhibit only one sharp resonance, indicating that the boron atoms are highly fluxional in solution. In contrast, two different boron resonances as expected for a rigid tricapped trigonal prism are clearly observed for the [B₉X₉]^2– dianions in solutions and for solid B₉Br₉ in the ¹¹B MAS NMR spectra. Temperature dependent ¹¹B MAS NMR experiments on B₉Br₉ and [B₉Br₉]^2– in the solid state show a reversible coalescence of the two resonances at higher temperature. ¹¹B MAS NMR spectra and DTA measurements of [B₉Br₉]^2– showed a phase transition.     

Copper complexes with N-allylisoquinolinium halides: Synthesis and crystal structures of [C9H7N(C3H5)]2CuIICl2.86Br1.14, [C9H7N(C3H5)CuIBr2] · H2O, and [C9H7N(C3H5)CuIBr2]

Crystals of the copper bromide complexes with N-allylisoquinolinium halides of the composition [C₉H₇N(C₃H₅)]₂Cu^IICl_2.86Br_1.14 (I), [C₉H₇N(C₃H₅)]Cu^IBr₂ · H₂O (II), and [C₉H₇N(C₃H₅)]Cu^IBr₂ (III) are prepared by ac electrochemical synthesis, and their structures are studied by X-ray diffraction analysis (DARCh-1 (for I) and KUMA/CCD (for II and III) diffractometers). The crystals of compound I are monoclinic: space group P2₁/n, a = 15.053(5) Å, b = 10.486(4) Å, c = 17.179(10) Å, γ = 109.77(3)°, V = 2552(4) ų, Z = 4. The crystals of complex II are triclinic: space group P $\overline 1 $ , a = 7.040(1) Å, b = 7.610(2) Å, c = 12.460(2) Å, α = 79.54(3)°, β = 86.73(3)°, γ = 89.51(1)°, V = 655.4(2) ų, Z = 2. The crystals of complex III are monoclinic: space group P2₁/n, a = 12.799(1) Å, b = 7.692(1) Å, c = 13.491(1) Å, β = 111.08(1)°, V = 1239.3(2) ų, Z = 4. The structure of compound I is built of the Cu^IIX ₄ ^2? tetrahedra and N-allylisoquinolinium cations united by the C-H···X contacts into corrugated layers. The crystal structure of π-complex II is formed of dimers of the composition [C₉H₇(C₃H₅)]₂ Cu ₂ ^I Br₄ forming layers in the direction of the z axis due to the C-H···X contacts. An important role in structure formation belongs to water molecules that cross-link the organometallic layers through the O-H···X contacts into a three-dimensional framework. When kept in the mother liquor for 6 months, the crystals of compound II transformed into crystals of compound III, whose structure consists of {[C₉H₇(C₃H₅)]₂Cu ₂ ^I Br₄} _n columns united through the C-H···Br contacts (H···Br 2.84(3)?2.92(4) Å) into a three-dimensional framework.     

Chemical vapor transport and solid-state exchange synthesis of new copper selenite bromides

A new dimorphic copper selenite bromide, Cu₅(SeO₃)₄Br₂ was obtained via chemical transport reactions. α-Cu₅(SeO₃)₄Br₂, monoclinic (1m) and β-Cu₅(SeO₃)₄Br₂, triclinic (1a) polymorphs were produced simultaneously upon reaction of amorphous, partially dehydrated copper selenite and copper bromide. 1m is similar to Cu₅(SeO₃)₄Cl₂, whereas 1a is distantly related to Ni₅(SeO₃)₄Br₂ and Co₅(SeO₃)₄Br₂. Attempts to reproduce synthesis of 1a via exchange reaction between Na₂SeO₃ and CuBr₂ resulted in a new Na₂[Cu₇O₂](SeO₃)₄Br₄ (2). Current study demonstrates for the first time, that both chemical vapor and exchange reactions can be employed in preparation of new selenite halides.     

Ethylene polymerization with novel bridged tri- and tetranuclear titanocene/MAO systems

Two benzene centered tri- and tetracyclopentadienyl ligands C₆H₃(CH₂C₅H₅)₃-1,3,5 (1) and C₆H₂(CH₂C₅H₅)₄-1,2,4,5 (2) and their titanium complexes C₆H₃[CH₂C₅H₄Ti(C₅H₅)Cl₂]₃-1,3,5 (3), C₆H₃[CH₂C₅H₄Ti(C₅H₄CH₃)Cl₂]₃-1,3,5 (4), as well as C₆H₂[CH₂C₅H₄Ti(C₅H₅)Cl₂]₄-1,2,4,5 (5) were synthesized and characterized by mass and ¹H NMR spectra. In the presence of methylaluminoxane (MAO), 3, 4 and 5 are efficient catalysts for ethylene polymerization in toluene. The influence of the polymerization conditions such as catalyst concentration, MAO/Ti molar ratio, polymerization time and temperature were investigated in detail. 3, 4 and 5 produce linear polyethylene (PE) with broad molecular weight distributions (MWD) and a little lower molecular weight.     

Two inclusion compounds of guanylthiourea and 1,3,5-thiadiazole-5-amido-2-carbamate

In the crystal structure of [(n-C₄H₉)₄N]⁺·[NH₂(C₂N₂S)NHCOO^?]·NH₂CSNC(NH₂)₂ (1), guanylthiourea molecules and 1,3,5-thiadiazole-5-amido-2-carbamate ions are joined together by intermolecular N–H…O, N–H…N, and weak N–H…S hydrogen bonds to generate stacked host layers corresponding to the (110) family of planes, between which the tetra-n-butylammonium guest cations are orderly arranged in a sandwich-like manner. In the crystal structure of [(n-C₃H₇)₄N]⁺·[NH₂(C₂N₂S)NHCOO^?]·NH₂CSNC(NH₂)₂·H₂O (2), the tetrapropyl ammonium cations are stacked within channels each composed of hydrogen bonded ribbons of guanylthiourea molecules, 1,3,5-thiadiazole-5-amido-2-carbamate ions and water molecules.