Synthese und Eigenschaften von TrimethyIstannylmethyl-Indium(III)-Verbindungen

Trimethyltin methyllithium reacts with InCl3, CH3InCl2 and R2InCl (R = CH3, t-C4H9) with formation of the new compounds In(CH2SnMe3)3, CH3In(CH2SnMe3)2, (CH3)2InCH2SnMe3 and (t-C4H9)2InCH2SnMe3. The compounds are characterized by elemental analyses, 1H, 13C, 119Sn NMR and IR spectra

Di-, Hexa- and Deca-Substituted Decaphenylferrocenes

5-Bromo-1,2,3,4-tetraphenyl-5-p-tolyl-1,3-cyclopentadiene (1a), 5-Bromo-1,4-di-phenyl-2,3,5- tri-p-tolyl-1,3-cyclopentadiene (1b), 5-Bromo-1,2,3,4,5-penta-p-tolyl-1,3-cyclopentadiene (1c), 5- Bromo-1,2,3,4-tetraphenyl-5-p-bromophenyl-1,3-cyclopentadiene (1d), and 5-Bromo-1,2,3,4-tetraphenyl- 5-p-anisyl-1,3-cyclopentadiene (1e) react with ironpentacarbonyl in m-xylene to yield the corresponding ferrocenes 2a - 2e. In the course of the purification procedure, reactions with HCl and the solvent m-xylene are observed which yield the mixed ionic sandwich complexes [(C5Ph4C6H4Me)Fe(C6H4Me2)]+Cl− (3a), [(C5Ph2(C6H4Me)3)Fe(C6H4Me2)]+Cl− (3b), [(C5(C6H4Me)5)Fe(C6H4Me2)]+Cl− (3c), [(C5Ph4C6H4Br)Fe(C6H4Me2)]+Cl− (3d), and [(C5Ph4 C6H4OMe)Fe(C6H4Me2)]+Cl− (3e), respectively, along with the corresponding cyclopentadienes 1,2,3,4-tetraphenyl-5-p-tolyl-1,3-cyclopentadiene (4a), 1,4-diphenyl-2,3,5-tri-p-tolyl-1,3- cyclopentadiene (4b), 1,2,3,4,5-penta-p-tolyl-1,3-cyclopentadiene (4c), 1,2,3,4-tetraphenyl-5-pbromphenyl- 1,3-cyclopentadiene (4d), and 1,2,3,4-tetraphenyl-5-p-anisyl-1,3-cyclopentadiene (4e). The compounds have been characterized by elemental analysis, IR, NMR, and mass spectra, and, in the case of 2c, by 13C-CPMAS spectroscopy and X-ray powder diffractometry

Metallorganische Verbindungen der Lanthanoiden, XTTT [1] Tris(di-f-butylarsin)-Derivate von Yttrium, Lanthan, Praseodym, Holmium, Erbium, Thulium und Lutetium

Lithium (di-t-butyl) arsenide reacts with the trichlorides of yttrium, lanthanum, praseodymium, holmium, erbium, thulium, and lutetium under elimination of lithium chloride and formation of the corresponding tris(di-t-butylarsine) derivatives

Synthese und Eigenschaften einiger neuer Organoindium-Methylenstannyl-Verbindungen

Im Zusammenhang mit unseren Arbeiten zur Herstellung leitfähiger Schichten für Flüssigkristall-Displays konnten wir kürzlich über die erstmalige Synthese metallorganischer Verbindungen berichten, die sowohl Zinn als auch Indium in einem Molekül enthalten, wie z.B. Me3SnCH2InMe2 [1]

Transition Metal and Lanthanide Complexes of 1,4,7,10-Tetraallyl- and 1,4,7,10-Tetra-3-butenyl- 1,4,7,10-tetraazacyclododecane

1,4,7,10-Tetraazacyclododecane (1) reacts with allylbromide and 3-butenylbromide giving 1,4,7,10-tetraallyl-1,4,7,10-tetraazacyclododecane (TAC) (2a) and 1,4,7,10-tetra-3-butenyl-1,4,7,10- tetraazacyclododecane (TBC) (2b), respectively. Compounds 2a and 2b react with FeCl2, CoCl2, RhCl3, NiCl2, CuBr2, and TmCl3 forming the complexes [FeCl(TAC)]Cl (3a), [FeCl(TBC)]Cl (3b), [CoCl(TAC)]Cl (4), [RhCl(TAC)]Cl2 (5), [NiCl(TAC)]Cl (6a), [NiCl(TBC)]Cl (6b), [CuBr(TAC)]Br (7), [TmCl(TAC)]Cl2 (8a), and [TmCl(TBC)]Cl2 (8b). The reaction of 6a with an excess of CuCl affords a coordination polymer in which [NiCl(TAC)]+ cations are connected by [Cu6Cl8]2− anions (9). The 1H and 13C NMR spectra of 2a, 2b, 5, and 6a, as well as the single crystal X-ray structures of 2a ・3HCl, 6a, 6b, 7, and 9 are reported and discussed

Deca(4-methylbenzyl)ferrocene and -stannocene

Cyclopentadiene reacts with five equivalents of 4-methylbenzylalcohol (1:5,6 mole ratio) and sodium yielding penta(4-methylbenzyl)cyclopenta-2,4-diene (1), which upon treatment with butyl lithium affords the lithium salt [(4-MeC6H4CH2)5C5]Li (2). The reactions of 2 with FeCl2 and SnCl2 result in the formation of deca(4-methylbenzyl)ferrocene (3) and deca(4-methylbenzyl)stannocene (4), respectively. The 1H and 13C NMR, IR and mass spectra of the new compounds as well as the single crystal X-ray structure analysis of 1 are reported and discussed

Electron Release and Proton Acceptance Reactions of (dpp-BIAN)Mg(THF)3

(dpp-BIAN)Mg(THF)3 (1) (dpp-BIAN = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) and (PhCOO)2 react with splitting of the peroxide bridge and formation of the dimeric magnesium benzoate [(dpp-BIAN)MgOCOPh(THF)]2 (2). The reaction of 1 with PhCOOH yields the dimeric magnesium benzoate [(dpp-BIAN)(H)MgOCOPh(THF)]2 (3), whereas 1 and furanyl-2-carboxylic acid react with liberation of hydrogen and formation of (dpp-BIAN)Mg[OCO(2-C4H3O)]2 Mg(dpp-BIAN)(THF) (4). Compounds 2, 3, and 4 have been characterized by elemental analysis, IR spectroscopy, and X-ray structure analysis, compound 3 also by 1H NMR spectroscopy. The eightmembered metallacycles of the centrosymmetric dimers 2 and 3 are almost completely planar. The two magnesium atoms in 4 show different coordination spheres; one is surrounded by its ligands in a trigonal bipyramidal manner, the other one in a tetrahedral fashion. The Mg···Mg separations in 2, 3 and 4 are 4.236, 4.296, and 4.030 Å, respectively

Fragmentable Heterogeneous Cocatalysts for the Metallocene-Catalyzed Polymerization of Olefins, I. Surface Modification of Silica and Characterization of the Resulting Carriers

Surface modification of pre-dried spherical silica nano-particles with diameters of 235 nm and 10 to 20 nm and of commercially available non-spherical silica materials using various aminoalkyltrialkoxysilanes and α-ω-bis(alkoxysilyl)organyls (organyl = alkanediyl, aminoalkanediyl, polyether, polysiloxane) has been performed in suspension in solvents with water. The quantity of water has a dominating influence, as compared to the amounts and the ratios of silanes employed, on the surface morphology of the modified silicas. The morphologies observed range from weakly linked aggregates of spherical particles to large agglomerates covered by thick irregular layers of organopolysiloxane, as demonstrated by scanning electron microscopy. These carriers can be modified further with organoaluminium compounds to yield heterogeneous cocatalysts for the polymerization of ethylene.BMBF, 03C0295, Verbundprojekt: Heterogene und homogene Cokatalysatoren und Katalysatoren für die OlefinpolymerisationDFG, GRK 352, Synthetische, mechanistische und reaktionstechnische Aspekte von Metallkatalysatore

Fragmentable Heterogeneous Cocatalysts for the Metallocene-Catalyzed Polymerization of Olefins, II [1]. Preparation, Characterization and Testing of the Cocatalysts and Microscopic Evaluation of the Polyethylene

Surface modified silica were reacted with different aluminiumalkyls AlR2R’ (R = Me, Et, i-Bu, R’ = H, Me, Et, i-Bu), oligomeric methylaluminoxane (MAO) and combinations of both, to yield heterogeneous cocatalysts. These cocatalyts were employed to polymerize ethylene using zirconocene dichloride as the catalyst. The polymerization activity profiles have been recorded and compared with the information gained from the scanning electron microscopy (SEM) images of the polymers. The fragmentation of the heterogeneous cocatalyts upon polymerization has been demonstrated. The degree of fragmentation and the polymerization activity depend on the preparation of the silica supports and on the preparation of the heterogeneous cocatalysts using these supports. The most reactive, fragmentable heterogeneous cocatalysts show polymerization activities slightly higher than MAO in homogeneous solution and almost 1.5 times higher than commercially available MAO on silica (=MAO on Sylopol).BMBF, 03C0295, Verbundprojekt: Heterogene und homogene Cokatalysatoren und Katalysatoren für die OlefinpolymerisationDFG, GRK 352, Synthetische, mechanistische und reaktionstechnische Aspekte von Metallkatalysatore

Organometallic Compounds of the Lanthanides, 41 [1]. The Crystal and Molecular Structure of (C5Me5)2HoCl(THF)

The title compound (1) is obtained as brownish crystals by reaction of HOCl3 with NaC5Me5 in tetrahydrofuran. The structure of 1, which has two slightly different independent molecules per asymmetric unit, has been elucidated by X-ray analysis. The crystals are triclinic with a = 1686.2(8) pm, b = 1816(1) pm, c = 846.5(4) pm, α = 92.02(7)°, β = 92.47(9)°, γ = 63.21(5)°, space group P1̄, D(calcd) = 1.560 g/cm3, and R = 0.0286, for 6219 observed reflections with I > 3σ(I)