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Philipp Willmes Dr. Michael J. Cowley Marco Hartmann Dr. Michael Zimmer Dr. Volker Huch Prof. Dr. David Scheschkewitz 《Angewandte Chemie (International ed. in English)》2014,53(8):2216-2220
The generation of heavier double‐bond systems without by‐ or side‐product formation is of considerable importance for their application in synthesis. Peripheral functional groups in such alkene homologues are promising in this regard owing to their inherent mobility. Depending on the steric demand of the N‐alkyl substituent R, the reaction of disilenide Ar2Si?Si(Ar)Li (Ar=2,4,6‐iPr3C6H2) with ClP(NR2)2 either affords the phosphinodisilene Ar2Si?Si(Ar)P(NR2)2 (for R=iPr) or P‐amino functionalized phosphasilenes Ar2(R2N)Si? Si(Ar)?P(NR2) (for R=Et, Me) by 1,3‐migration of one of the amino groups. In case of R=Me, upon addition of one equivalent of tert‐butylisonitrile a second amino group shift occurs to yield the 1‐aza‐3‐phosphaallene Ar2(R2N)Si? Si(NR2)(Ar)? P?C?NtBu with pronounced ylidic character. All new compounds were fully characterized by multinuclear NMR spectroscopy as well as single‐crystal X‐ray diffraction and DFT calculations in selected cases. 相似文献
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Novel structures of H2C?C?CLiX (X ? F, Cl) were determined using HF/STO-3G gradient method. Both of the carbenoids have two equilibrium structures, askew and linear forms, at the level of calculation. In the case X?F, the former is more stable, but in the case X=Cl, the latter is more stable. The frontier MOs are given and analyzed. 相似文献
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Alternative Ligands. XXVI. M(CO)4 L-Complexes (M ? Cr, Mo, W) of the Chelating Ligands Me2ESiMe2(CH2)2E′ Me2 (Me ? CH3; E ? P, As; E′ ? N, P, As) The reaction of M(CO)4NBD (NBD = norbornadiene; M ? Cr, Mo, W) with the ligands Me2ESiMe2(CH2)2E′ Me2 yields the chelate complexes (CO)4M[Me2ESiMe2]) for E,E′ ? P, As, but not for E and /or E′ ? N. The NSi group is not suited for coordination because of strong (p-d)π-interaction. In the case of the ligands with E ? P or As and E′ ? N chelate complexes can be detected in the reaction mixture, but isolable products are complexes with two ligands coordinated via the E donor group. The new compounds are characterized by analytical and spectroscopic (IR, NMR, MS) investigations. The spectroscopic data are also used to deduce the coordinating properties of the ligands. X-ray diffraction studies of the molybdenum complexes (CO)4Mo[Me2ESiMe2(CH2)2AsMe 2] (E ? P, As) in accord with the observed coordination effects show only small differences between SiE and CE donor functions. Attempts to use the ligands Me2ESiMe2(CH2)2AsMe2 (E ? P, As) for the preparation of Fe(CO)3L complexes result in the fission of the SiE bonds and the formation of the binuclear systems Fe2(CO)6(EMe2)2 (E ? P, As) together with the disilane derivative [Me2Si(CH2)2AsMe2]2. 相似文献
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T. A. Sukhova A. N. Panin O. N. Babkina N. M. Bravaya 《Journal of polymer science. Part A, Polymer chemistry》1999,37(8):1083-1093
Catalytic activity of Me2SiCp*NtBuMX2/(CPh3)(B(C6F5)4) [MTi, XCH3 (1); MZr, X=iBu (2)] systems in the ethylene/styrene (E/S) feed was examined. Experimental data revealed high activity for the catalytic system (1) for copolymerization ethylene with styrene, whereas the system with enhanced catalytic activity for ethylene homopolymerization (2) was temporarily blocked in the styrene presence yielding, even at high styrene content, homopolyethylene as the final product. Properties of thus obtained polymers were analyzed. Catalytic system (1) occurred very sensitive to S/E ratio in the comonomers feed. The 10‐fold acceleration for ethylene consumption was shown in two experimental sets conducted at S/E = 1.3 ratio, 1 bar, and 7.5 bar ethylene pressure, respectively. The consequent enhancement in S/E ratio resulted in slowing down both ethylene consumption and catalyst deactivation rates. Atactic polystyrene was formed at high styrene content with the catalyst (1). Catalytic system (1) allowed design of products with the highest styrene content (20 mol %) at low ethylene pressure, moderate temperature, and high S/E ratio. The apparent activation energy estimated from the initial rates of ethylene consumption was 54.6 kJ/mol. Analysis of apparent reactivity factors (rE = 9 and rS = 0.04; rE × rS = 0.4) and 13C‐NMR copolymer spectra revealed an alternating tendency of the comonomers for active center incorporation. DSC measurements showed considerable decrease of melting points and crystallinity even for copolymers with low styrene content. The catalyst produced relatively high–molecular weight copolymers (140–150 kg/mol) even at 80°C. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1083–1093, 1999 相似文献
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