2,2,4,4-Tetramethyl-2,4-disila-cyclo-butylzinkchlorid · TMEDA und verwandte Verbindungen

2,2,4,4-Tetramethyl-2,4-disila-cyclo-butylzinc Chloride · TMEDA and Related Compounds The reaction of (tmeda)lithium 2,2,4,4-tetramethyl-2,4-disila-cyclo-butanide with anhydrous zinc(II) chloride in pentane in the molar ratio of 2:1 does not yield the expected dialkylzinc derivative but the monosubstitution product 2,2,4,4-Tetramethyl-2,4-disila-cyclo-butylzinc chloride · tmeda 1 . This derivative crystallizes in the orthorhombic space group Pnma with a = 1 235.0(1); b = 1 696.8(2); c = 1 148.0(1) pm and Z = 4. The Zn? C bond lengths lie with 198,4 pm in the characteristic region for compounds containing a tetrahedrally coordinated zinc atom. The thermolysis of 1 leads under elimination of ZnCl₂ to the formation of Bis(2,2,4,4-tetramethyl-2,4-disila-cyclo-butyl)zinc · tmeda 2 . (tmeda)LiCH(SiMe₃)₂ reacts analogously with one equivalent of ZnCl₂ to Bis(trimethylsilyl)methylzinc chloride · tmeda 3 . Lithium methanide or Lithium butanide add to a Si-C bond of 1,1,3,3-tetramethyl-1,3-disila-cyclo-butane, and these acyclic lithium alkanides 4 ( a : R = Me, b : R = n-Bu) yield with zinc(II) chloride the destillable dialkyl zinc compounds Bis(2,2,4,4-tetramethyl-2,4-disilapentyl)- 5 a and Bis(2,2,4,4-tetramethyl-2,4-disila-octyl)zinc 5 b .     

Synthese,Eigenschaften und Struktur von Amin-Addukten der Lithium-tris[bis(trimethylsilyl)methyl]zinkate

Synthesis, Properties, and Structure of the Amine Adducts of Lithium Tris[bis(trimethylsilyl)methyl]zincates . Bis[bis(trimethylsilyl)methyl]zinc and the aliphatic amine 1,3,5-trimethyl-1,3,5-triazinane (tmta) yield in n-pentane the 1:1 adduct, the tmta molecule bonds as an unidentate ligand to the zinc atom. Bis[bis(trimethylsilyl)methyl]zinc · tmta crystallizes in the triclinic space group P1 with {a = 897.7(3); b = 1 114.4(4); c = 1 627.6(6) pm; α = 90.52(1); β = 103.26(1); γ = 102.09(1)°; Z = 2}. The central C₂ZnN moiety displays a nearly T-shaped configuration with a CZnC angle of 157° and Zn? C bond lengths of 199 pm. The Zn? N distances of 239 pm are remarkably long and resemble the loose coordination of this amine; a nearly complete dissociation of this complex is also observed in benzene. The addition of aliphatic amines such as tmta or tmeda to an equimolar etheral solution of lithium bis(trimethylsilyl)methanide and bis[bis(trimethylsilyl)methyl]zinc leads to the formation of the amine adducts of lithium tris[bis(trimethylsilyl)methyl]zincate. Lithium tris[bis(trimethylsilyl)methyl]zincate · tmeda · 2 Et₂O crystallizes in the orthorhombic space group Pbca with {a = 1 920.2(4); b = 2 243.7(5); c = 2 390.9(5) pm; Z = 8}. In the solid state solvent separated ions are observed; the lithium cation is distorted tetrahedrally surrounded by the two nitrogen atoms of the tmeda ligand and the oxygen atoms of both the diethylether molecules. The zinc atom is trigonal planar coordinated; the long Zn? C bonds with a value of 209 pm can be attributed to the steric and electrostatic repulsion of the three carbanionic bis(trimethylsilyl)methyl substituents.     

Das Valenzkraftfeld des Dimethyl-nitrosamins

Ohne Zusammenfassung     

Vergleichende Untersuchungen zur Silicationenkonstitution in [(Ethyl)n(2-hydroxyethyl)4−nammonium]-Silicatlösungen mit n von 3 bis 1 und zum Einfluß von Alkalihydroxid

Comparing Investigations on the Silicate Constitution in [(Ethyl)_n(2-hydroxyethyl)_4?n-ammonium] Silicate Solutions with n from 3 to 1 and on the Influence of Alkali Hydroxide In [(ethyl)_n(2-hydroxyethyl)_4?nammonium]-silicate solutions with n from 3 to 1, free of alkali hydroxides, double three-ring and double four-ring silicate anions are to be found. With a growing number of 2-hydroxyethyl groups contained in the ammonium ion, the part of double four-ring ions increases. Other influating factors are the molar ratio of organoammonium hydroxide to silicon dioxide and the SiO₂-concentration. Admixtures of alkali hydroxides modify the ratio of double three-ring to double four-ring ions and cause also a degradation of both kinds of silicate ions, the effect of sodium hydroxide surpassing that of potassium hydroxide.     

Über die asymptotische Verteilung gewisser konvergenzerzeugender Faktoren

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Numerical shaper optimization for sputtered optical precision filters

A novel optimization procedure for optical precision sputter coaters with respect to the film homogeneity is demonstrated. For a coater concept based on dual cylindrical sputtering sources and a rotating turn-table as sample-holder, the inherent radial decay of the film thickness must be compensated by shaper elements. For that purpose, a simulation model of the particle flux within such a coater is set up and validated against experimental data. Subsequently, the shaper design is optimized according to the modeled metal flux profile. The resulting film thickness deviations are minimized down to ±0.3.5%     

Structural chemistry of polycyclic heteroaromatic compounds. Part XI. Photoelectron spectra and electronic structures of tetracyclic hetarenes of the triphenylene type

The UV photoelectron spectra of several tetracyclic heteroaromatic compounds (2-9) which are pi-isoelectronic with triphenylene (1) have been recorded and analysed making use of semiempirical AM1 and PM3 as well as ab initio/DFT B3LYP calculations. In one series of compounds (2-7), the peripheral benzene rings of 1 are successively substituted by thiophene rings that are either [b]- or [c]-annellated with the central benzene unit. In 2-7 only marginal shifts are found for most of the IPs of electrons. In the benzotrithiophenes 5-7, a systematic variation is displayed by IP(pi7). Compared to 1, the pi electron system of benzo[c]trithiophene (7) is approximately two times as much destabilized as in the isomers 5 and 6 with [b]annellated thiophene rings. The IP[n(S)] values of the thiophene derivatives 2-7 indicate that these orbitals are clearly destabilized relative to thiophene. The same holds for the n(O) orbital of the furane derivative 9 in comparison with that of furane. In 9, only the higher pi MOs (pi7-pi9) are destabilized whereas the lower levels (pi1-pi4) are stabilized, and those in between (pi5-pi6) remain essentially unshifted. In the pyrrole derivative 8, all pi MOs are substantially destabilized by about 0.5-1.6 eV relative to 1.     

Photoelectron spectra and electronic structure of some 4-substituted 2-allylanisoles

The electronic structures of 4-substituted 2-allyl anisoles (1-9) have been investigated by ultraviolet photoelectron spectroscopy and quantum chemical methods. The ionisation potentials corresponding to the pi MOs pi(2) and pi(3) of the phenyl ring, and the n(O) orbital of the methoxy group as well as the allylic pi(C=C) orbital could be determined and assigned for 1-9. Linear regression analyses of the IPs related to these orbitals with different substituent constants indicated that Hammett sigma(p) values performed satisfactorily to fair for pi(2), pi(3) and n(O) but poor for allylic pi(C=C). Other substituent constants such as R and R(-) were fair only for pi(2) and pi(3), but poor for n(O) and pi(C=C).