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91.
Synthesis and inversion barriers of undeca- and dodeca-substituted saddle shaped porphyrin complexes
Synthesis and barriers to inversion of a series of highly saddle shaped complexes are reported. The ΔG≠ has decreased by 8 kJ mol−1 at 243 K when the meso phenyl groups are replaced by bulkier 2,6-dichlorophenyl groups, and by 17 kJ mol−1 when one of the peripheral ethyl groups is removed. 相似文献
92.
Takakazu Yamamoto Junichi Ishizu Sanshiro Komiya Yoshiyuki Nakamura Akio Yamamoto 《Journal of organometallic chemistry》1979,171(1):103-112
13C NMR data are given for a series of phosphinenickel(0) complexes of ethyl methacrylate (ema), Ni(PR3)2(CH2=C(CH3)COOC2H5) (PR3 = PPh3 (Ia), PEtPh2 (Ib), PEt2Ph (Ic), PMe2Ph (Id), PEt3 (Ie)). The olefinic carbon signals of ema shift upfield by 71.5–86.5 ppm on coordination, the magnitude of the upfield shift increasing with increase in the bacisity of the phosphine ligand. The effect of the basicity of PR3 is discussed on the basis of the back-bonding from Ni to ema. Variable temperature1H NMR studies reveal that the ema of Id, the complex having the least sterically demanding phosphine ligands, exchanges with free ema in toluene on the NMR time scale. The dependence of the rate of exchange on the concentration of ema shows that the exchange proceeds through anSN2 mechanism. The activation parameters are: ΔH273≠ 2.75 kcal/mol, ΔG273≠ 12.7 kcal/mol, ΔS273≠ ?37 e.u. The31P NMR spectra of the complexes show two doublets when the exchange is frozen out, indicating the inequivalence of the two phosphine ligands in the ema-coordinated complex. The difference in the31P chemical shifts of the two coordinated tertiary phosphines increases with increase in the basicity of the PR3 ligand. 相似文献
93.
Shu Nakamura 《Communications in Mathematical Physics》1994,161(1):63-76
Low energy behavior of Schrödinger operators with potentials which decay slowly at infinity is studied. It is shown that if the potential is positive then the zero energy is very regular and the resolvent is smooth near 0. This implies rapid local decay for the solutions of the Schrödinger equation. On the other hand, if the potential is negative then the resolvent has discontinuity at zero energy. Thus one cannot expect local decay faster than ordert
–1 ast. 相似文献
94.
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96.
Tadashi Kon Tetsuro Kobayashi Shoichi Kitamura Keiichiro Nakamura Shunji Adachi 《Zeitschrift fur Physik C Particles and Fields》1994,61(2):239-246
In the framework of the minimal supersymmetric standard model (MSSM) and theR-parity breaking model (RBM), we investigate production processes of the scalar top (stop) at HERA energies. These models are characterized by the possible existence of the light stop whose mass is lighter than those of the top quark and the other squarks. It is shown that in the MSSM the stop pair production via boson-gluon fusion gives a sizeable cross section and the most serious background $ep \to ec\bar cX$ could be suppressed by appropriate kinematical cuts. We also show that in the RBM the stop is singly produced in the neutral current processes and we have a clear signal as a sharp peak in the Bjorken parameterx distribution of the scattered electron. 相似文献
97.
Mössbauer spectra of ferrocene derivatives in the solid, adsorption and liquidcrystalline states were measured at temperatures ranging from 78 to 423 K. The peak intensities of the Mössbauer spectra of ferrocene derivatives adsorbed on silica gel decreased markedly with an increase in temperature. The Mössbauer absorption of [4-(4-methoxyphenoxycarbonyl)-phenoxycarbonyl]alkyl 4-ferrocenylbenzoate at 295 K during the cooling process was observed in what was assumed to be the liquid-crystalline state. 相似文献
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