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961.
962.
963.
The Reaction of Dialkylaluminium Chlorides with Bis(trimethylsilyl)hydrazine: Formation of the Adducts R2AlCl · NH2NHSiMe3 Containing the Unstable Monotrimethylsilylhydrazine Bis(trimethylsilyl)hydrazine did not react with dialkylaluminium chlorides R2AlCl [R = CH2CMe3, CMe3 and CH(SiMe3)2] by the formation of trimethylchlorosilane, but by dismutation to yield tris(trimethylsilyl)hydrazine and trimethylsilylhydrazine. The unstable, sterically less shielded NH2NHSiMe3 was stabilized by the coordination to the coordinatively unsaturated aluminium compounds. The adducts R2AlCl · NH2NHSiMe3 were formed, which were characterized by crystal structure determinations with R = CMe3 and CH(SiMe3)2. In all cases, the hydrazine derivative binds to the aluminium atoms via the more basic NH2 nitrogen atom. The adduct Me3CAlCl2 · NH2N(SiMe3)2 containing intact 1,1‐bis(trimethylsilyl)hydrazine as a ligand was isolated in a trace amount and also characterized by a crystal structure determination. 相似文献
964.
[ScCl2{N(SiMe3)2}(THF)2] – a Precursor for the Synthesis of Scandium Nitride [ScCl2{N(SiMe3)2}(THF)2] ( 1 ) has been prepared by the reaction of [ScCl3(THF)3] with the trisamide Sc[N(SiMe3)2]3 in tetrahydrofurane solution forming colourless moisture sensitive crystals, which were characterized by a crystal structure determination. Space group P 1, Z = 2, lattice dimensions at –50 °C: a = 841.4(1), b = 924.2(1), c = 1550.0(1) pm, α = 90.046(7)°, β = 95.671(9)°, γ = 106.066(6)°, R1 = 0.0329. In the molecular structure of 1 the scandium atom has a distorted trigonal‐bipyramidal coordination with the THF molecules in apical positions. At 400 °C 1 is converted into scandium nitride, ScN, by stepwise leaving of THF and ClSiMe3. 相似文献
965.
Ulrike Riese Naim Faza Werner Massa Klaus Harms Thees Breyhan Paul Knochel Jürgen Ensling Vadim Ksenofontov Philipp Gütlich Kurt Dehnicke 《无机化学与普通化学杂志》1999,625(9):1494-1499
The phosphoraneiminato complexes [MnBr(NPEt3)]4 ( 1 ) and [M4Br5{NP(NMe2)3}3] with M = Mn ( 2 ) and M = Co ( 3 ) are prepared by melting reactions from the anhydrous metal dibromides with the silylated phosphaneimines Me3SiNPR3 (R = Et, NMe2) in the presence of potassium fluoride. All complexes are characterized by crystal structure analyses. 1 forms an only slightly distorted Mn4N4 heterocubane skeleton with an approximate Td symmetry and short Mn…Mn distances of average 295.7 pm. In the structures of 2 and 3 one μ3-NPEt3 ligand of 1 is replaced by one bromine atom with μ3-function. This leads to the novel heterocubane type M4N3Br with approximate C3 symmetry. The deformation of the cubic skeleton leads to metal-metal distances of different lengths, i. e. 292.7 and 323.6 pm in 2 and 274.4 and 306.2 pm in 3 . Temperature dependent magnetic susceptibility measurements between 300 and 5 K on 1 have shown that strong antiferromagnetic coupling exists between the Mn(II) ions with S = 5/2, with a large negative Weiss constant of Θ = –694 K. 相似文献
966.
Marc Karl Klaus Harms Gerd Seybert Werner Massa Stefan Fau Gernot Frenking Kurt Dehnicke 《无机化学与普通化学杂志》1999,625(12):2055-2063
Deprotonation Reactions of Silylated Amido Complexes of Rare Earth Elements The deprotonation of the rare earth element-tris(bistrimethylsilyl)amides Ln[N(SiMe3)2]3 of scandium, ytterbium, and lutetium with sodium-bis(trimethylsilyl)amide in THF leads to the complexes [Na(THF)3LnCH2SiMe2NSiMe3{N(SiMe3)2}2] [Ln = Sc ( 1 ), Yb ( 2 ), and Lu ( 3 )]. According to crystal structure analyses of 1 and 2 the metal atoms Sc and Yb are constituents of planar LnCSiN four-membered rings. At the same time, the C atom of the CH2 group is coordinated with the sodium ion in a linear axis Ln–C–Na; the sodium ion obtains a distorted tetrahedral arrangement by three THF molecules. The equatorial positions of the methylene-C atom, which is coordinated in a trigonal bipyramidal fashion, are occupied by the two H atoms and the Si atom of the four-membered ring. 2.6-dimethylbenzoisonitrile can be inserted into the Yb–CH2 bond of 2 and the new five-membered heterocylce YbNCSiN originates, the exocyclic CH2 group of which enters into a C–C coupling with the centrosymmetric dimer 4 while the ytterbium undergoes reduction. At the same time, sodium-7-methyl indolate is formed, which together with [NaN(SiMe3)2(THF)2] forms the centrosymmetric dimeric molecular aggregate [NaN(SiMe3)2(THF)2Na(C9H16N)]2 ( 5 ). 1 : Space group P21/n, Z = 8, lattice dimensions at –80 °C: a = 2941.4(2), b = 1205.5(1), c = 2952.4(3) pm; β = 113.455(8)°; R1 = 0.0625. 2 : Space group P21/n, Z = 8, lattice dimensions at –80 °C: a = 2943.9(1), b = 1219.5(1), c = 2944.3(1) pm; β = 113.372(4)°; R1 = 0.0361. 4 : Space group P 1, Z = 4, lattice dimensions at –80 °C: a = 1117.0(1), b = 1207.5(1), c = 1614.3(2) pm; α = 73.634(10)°, β = 82.091(10)°, γ = 74.391(10)°; R1 = 0.0525. 5 : Space group P21/n, Z = 2, lattice dimensions at –80 °C: a = 1126.7(1), b = 1459.3(1), c = 1741.1(1) pm; β = 96.461(8)°; R1 = 0.0458. Quantum chemical DFT calculations of the scandium model compound [Na(Me2O)3ScCH2SiMe2NSiH3{N(SiH3)2}2] ( 1 M ) give a very large negative charge at the pentacoordinated carbon atom of the four-membered ring that is concentrated in a lone-pair orbital which has mainly p character. The carbon atom interacts with the positively charged scandium atom mainly by Coulombic interactions. 相似文献
967.
Nils Wiberg Hans-Wolfram Lerner Heinrich Nth Werner Ponikwar 《Angewandte Chemie (International ed. in English)》1999,38(8):1103-1105
Dark violet hexastannane ( t Bu 3 Si) 6 Sn 6 displays a new framework motif for molecular tin compounds, in which six Sn atoms are located at the corners of a trigonal prism. The compound can be synthesized according to Equation (a). R*=SitBu3. 相似文献
968.
Ulrich Herber Birgit Weberndrfer Helmut Werner 《Angewandte Chemie (International ed. in English)》1999,38(11):1609-1613
Significantly different coordination spheres are displayed by the two central atoms of 2 , the first representative of a novel type of mixed-valence dinuclear Rh0–RhII compound, which was synthesized from the stibane-bridged complex 1 . The Rh−Rh distance determined by an X-ray crystal structure analysis of 2 indicates a metal–metal interaction between the two metal centers. 相似文献
969.
David Scheschkewitz Matthias Menzel Matthias Hofmann Paul von Ragu Schleyer Gertraud Geiseler Werner Massa Klaus Harms Armin Berndt 《Angewandte Chemie (International ed. in English)》1999,38(19):2936-2939
Remarkably short distances to the ring plane are shown by the η5-bound lithium ions in the first compound with a triply negatively charged five-membered ring, 1 , which was obtained by reduction of 2 with lithium. R=CH(SiMe3)2, Dur=2,3,5,6-tetramethylphenyl. 相似文献
970.
Linda Didaoui A. Touabet A. Y. Badjah Hadj Ahmed B. Y. Meklati Werner Engewald 《Journal of separation science》1999,22(10):559-564
In reversed phase liquid chromatography (RP-HPLC), the validity of a multiparametric non-linear least-squares regression iterative method for the determination of the column dead time tM and the regression parameter (slope b), based on the use of alkan-2-ones, alkyl aryl ketones, and 1-nitroalkanes has been evaluated. The determination of tM and b has been extensively studied for two mobile phase systems acetonitrile-water and methanol-water on seven octadecyl-C18 and one octyl C8 analytical columns. The calculated tM and b values were compared with those obtained by Guardino's and Grobler's methods. The influence exerted thereon by the nature of the homologous series, the mobile phase composition, and the packing materials were investigated. 相似文献