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991.
992.
[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
993.
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
994.
Shunichi Fukuzumi Ikuo Nakanishi Jean-Michel Barbe Roger Guilard Eric Van Caemelbecke Ning Guo Karl M. Kadish 《Angewandte Chemie (International ed. in English)》1999,38(7):964-966
Slow electron transfer to manganese(iii) porphyrins results when the macrocycle deviates from planarity. This was demonstrated by measuring the kinetics of homogeneous electron transfer from a series of semiquinone radical anions to synthetic manganese porphyrins (shown schematically; R1=H, Cl, F; R2=H, F). Three of the four porphyrins studied have nonplanar macrocycles. These results could have implications for the role of manganese in biological electron transfer processes. 相似文献
995.
Karl A. Scheidt Akihiro Tasaka Thomas D. Bannister Michael D. Wendt William R. Roush 《Angewandte Chemie (International ed. in English)》1999,38(11):1652-1655
A careful orchestration of protecting groups is an essential requirement for the total synthesis of the macrolide antibiotic bafilomycin A1 ( 1 ). Key steps were the Suzuki cross-coupling reaction of two advanced, suitably protected intermediates prior to closure of the macrocycle, as well as a highly stereoselective methyl ketone aldol reaction. 相似文献
996.
Alfred L. Yergey A. Karl Yergey 《Journal of the American Society for Mass Spectrometry》1997,8(9):943-953
Calutrons were developed in the laboratory of E. O. Lawrence at the University of California at Berkeley. They were a modification of the cyclotrons he had invented and used in his Noble Prize winning investigations of the atomic nucleus. At the time their construction was undertaken, calutrons represented the only certain means of preparing enriched uranium isotopes for the construction of a fission bomb. The effort was successful enough that every atom of the 42 kg of 235U used in the first uranium bomb had passed through at least one stage of calutron separation. At peak production, the first stage separators, α tanks, yielded an aggregate 258-g/d 235U enriched to about 10 at. % from its natural abundance level of 0. 72 at. %. The second stage separators, β tanks, used the 10 at. % material as feedstock and produced a total 204-g/d 235U enriched to at least 80 at. %. The latter, weapons grade, material was used in fission bombs. Under typical operating conditions, each α tank operated at a uranium beam intensity at the collectors of approximately 20 mA and each β tank at a beam intensity of approximately 215 mA at the collectors. Bulk separation of isotopes for bomb production ceased in 1945. Since that time calutrons have been used to separate stable isotopes, but on a more limited scale than wartime weapons production. Stable isotope separations since 1960 have taken place using one modified beta tank. 相似文献
997.
Thierry Sifferlen Magnus Rueping Karl Gademann Bernhard Jaun Dieter Seebach 《Helvetica chimica acta》1999,82(12):2067-2093
To test the effect of NH−C=S groups (Scheme 1) on the stability of β-peptide secondary structures, we have synthesized three β-thiohexapeptide analogues of H-(β-HVal-β-HAla-β-HLeu)2-OH ( 1 ) with one, two, and three C=S groups in the N-terminal positions (cf. 2 – 4 and model in Fig. 1). The first C=S group was introduced selectively by treatment with Lawesson reagent of Boc-β-dipeptide esters ( 6 and 8 ). A series of fragment-coupling steps (with reagents as for the corresponding sulfur-free building blocks) and another thionation reaction led to the title compounds with a C=S group in residues 1, 1, and 3, as well as 1, 2, and 3 of the β-hexapeptide (Schemes 2 and 3). The sulfur derivatives, especially those with three C=S groups, were much more soluble in organic media than the sulfur-free analogues (>1000-fold in CHCl3; Table 1). The UV and CD spectra (in CHCl3, MeOH, and H2O) of the new compounds were recorded and compared with those of the parent β-hexapeptide 1 (Figs. 2 – 4); they indicate the presence of more than one secondary structure under the various conditions. Most striking is a pronounced exciton splitting (Δλ ca. 20 nm, amplitude up to +121000) of the ππ*C=S band near 270 nm with the β-trithiohexapeptide (with and without terminal protecting groups), and strong, so-called `primary solvent effects', in the CD spectra. The CD spectrum of the β-dithiohexapeptide 3 undergoes drastic changes upon irradiation with 266-nm laser light of a MeOH solution (Fig. 5). The NMR structure in CD3OH of the unprotected β-trithiohexapeptide 4 was determined to be an (M)-314-helix (Fig. 7), very similar to that of the non-thionated analogue (cf. 1 ). NMR and mass spectra of the β-hexapeptides with C=S and with C=O groups are compared (Figs. 6 and 8). 相似文献
998.
999.
The recent development of surface growth studies using X‐ray photon correlation spectroscopy in a grazing‐incidence small‐angle X‐ray scattering (Co‐GISAXS) geometry enables the investigation of dynamical processes during kinetic roughening in greater detail than was previously possible. In order to investigate the Co‐GISAXS behavior expected from existing growth models, calculations and (2+1)‐dimension simulations of linear Kuramoto–Sivashinsky and non‐linear Kardar–Parisi–Zhang surface growth equations are presented which analyze the temporal correlation functions of the height–height structure factor. Calculations of the GISAXS intensity auto‐correlation functions are also performed within the Born/distorted‐wave Born approximation for comparison with the scaling behavior of the height–height structure factor and its correlation functions. 相似文献
1000.
Biehl et al. (2021) present some interesting observations on an early formulation of the free energy principle. We use these observations to scaffold a discussion of the technical arguments that underwrite the free energy principle. This discussion focuses on solenoidal coupling between various (subsets of) states in sparsely coupled systems that possess a Markov blanket—and the distinction between exact and approximate Bayesian inference, implied by the ensuing Bayesian mechanics. 相似文献