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31.
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33.
Cobalt‐Catalyzed Intramolecular Reactions between a Vinylcyclopropane and an Alkyne: Switchable [5+2] Cycloaddition and Homo‐Ene Pathways
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Dr. Chunlin Wu Prof. Dr. Naohiko Yoshikai 《Angewandte Chemie (International ed. in English)》2018,57(22):6558-6562
Cobalt–diphosphine catalysts have been found to promote intramolecular reactions between a vinylcyclopropane and an alkyne to selectively afford either the [5+2] cycloaddition product or the homo‐ene reaction product under solvent control. The former product is exclusively formed in noncoordinating 1,2‐dichloroethane, whereas the latter is dominant in coordinating solvents, such as acetonitrile and dimethylacetamide. Furthermore, a highly enantioselective variant of the homo‐ene reaction afforded chiral tetrahydrofuran, pyrrolidine, and cyclopentane derivatives bearing 1,3‐diene and alkylidene substituents. 相似文献
34.
Nakano K Suemura N Kawata S Fuyuhiro A Yagi T Nasu S Morimoto S Kaizaki S 《Dalton transactions (Cambridge, England : 2003)》2004,(7):982-988
The synthesis and characterization of new spin-crossover pyrazolato bridged dinuclear [(FeII(NCS)(py))2(mu-bpypz)2] and the corresponding cyanotrihydroborato-kappaN complexes are described together with the X-ray crystal analysis of the latter in both the high-spin and low-spin states as well as the variable temperature magnetic susceptibility and/or Mossbauer spectra demonstrating the spin-crossover which exhibits an one-step process, but not a two-step one characteristic of the known bpym bridged dinuclear complexes. 相似文献
35.
Ishikawa H Sugiyama M Baba I Setaka W Kira M Mikami N 《The journal of physical chemistry. A》2005,109(40):8959-8961
An equilibrium structure of the charge-transfer (CT) state of (p-cyanophenyl)pentamethyldisilane was determined by transient infrared absorption spectroscopy of its CH stretching vibration region, and by the spectral simulation with quantum chemical calculations. It was found that a pattern of the CH stretching vibration bands of the CT state is substantially different from that of the S0 state. This band feature of the CT state was well reproduced assuming the planar sigma(Si-Si)pi* state, where the disilanyl group and the phenyl ring lie in the same plane. Considering that the disilanyl group in the S0 and the locally excited pipi* states lie in the plane perpendicular to the phenyl ring, an occurrence of a twisting-type structural change during the ICT process was experimentally identified in the present study. 相似文献
36.
Takayuki Ebata Kei Saito Haruki Ishikawa Naohiko Mikami 《Research on Chemical Intermediates》1998,24(8):803-812
The S1−S0 electronic spectrum of methyl cinnamate in a supersonic jet has been investigated to discriminate the transitions of the
s-cis/s-trans conformers. Population labelling spectroscopy was applied to the conformer discrimination, and vibronic bands belonging to
each conformer were identified. The relative population was estimated from the fluorescence quantum yields obtained by lifetime
measurements. It was found that both conformers exist almost equally in a supersonic jet. The conformer identification of
the vibronic bands was carried out based on the difference of the red-shift of their hydrogen-bonded complexes with methanol. 相似文献
37.
The separation of normolipidemic male serum lipoprotein fraction, prepared by ultracentrifugal flotation, was studied on hydroxyapatite columns. Potassium phosphate buffers in the pH range 5.6-7.4 were evaluated as eluents. The three main classes of the lipoproteins (high density, low density and very low density) can be separated on the Tiselius-type hydroxyapatite (Bio-Gel HTP DNA grade) column by elution with 75, 250 and 300 mM potassium phosphate buffer (pH 7.4), respectively. 相似文献
38.
The structures and reactivities of the complexes between carbenium ions (R(+)) and acetylene or propyne have been investigated with the aid of electron-correlated quantum mechanical calculations (hybrid density functional, perturbation theory, and coupled cluster methods). Depending on the R group, the acetylene/carbenium ion interaction can produce either an "open" 3c-2e structure or the conventional vinyl cation structure. The "open" 3c-2e C-C-C bonding geometry exists as a minimum for R = methyl and primary/secondary/tertiary alkyl, and hence is the most notable. The alignment of three carbon centers is neither bridged nor linear, but L-shaped, and represents a new type of "open" 3c-2e bonding that has so far escaped proper attention. 相似文献
39.
The microsolvation structure of the [benzene-(methanol)(n)](+) (n = 1-6) clusters was analyzed by electronic and infrared spectroscopy. For the n = 1 and 2 clusters, further spectroscopic investigation was carried out by Ar atom attachment, which has been know as a useful technique for discriminating isomers of the clusters. The coexistence of multiple isomers was confirmed for the n = 1 and 2 clusters, and remarkably, preferential production of the specific isomers occurred in the Ar attachment. The most stable isomer of the n = 1 cluster was suggested to be of the "on-ring" structure where the nonbonding electrons of the methanol moiety directly interact with the pi orbital of the benzene cation moiety. This is a sharp contrast to [benzene-(H(2)O)(1)](+), exhibiting the "side" structure, where the water moiety is bound to the C-H sites of the benzene cation moiety. The structure of the n = 2 cluster was discussed with the help of density functional theory calculations. Spectral signatures of the intracluster proton-transfer reaction were found for n > or = 5. The intracluster electron-transfer reaction leading to the (methanol)(m)()(+) fragment was also seen upon vibrational and electronic excitation of n > or = 4. 相似文献
40.
Preparation of ureido group bearing polymers and their upper critical solution temperature in water
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Ami Fujihara Kohei Itsuki Naohiko Shimada Atsushi Maruyama Naoya Sagawa Toshiyuki Shikata Shin‐Ichi Yusa 《Journal of polymer science. Part A, Polymer chemistry》2016,54(18):2845-2854
Poly(2‐ureidoethylmethacrylate) (PUEMn) was synthesized via reversible addition‐fragmentation chain transfer (RAFT) radical polymerization and following polymer reaction. We prepared two PUEMn samples with different degrees of polymerization (n = 100 and 49). The polymers exhibited upper critical solution temperature (UCST) in phosphate‐buffered saline (PBS) solution. The phase separation temperature (Tp) in PBS can be controlled ranging from 17 to 55 °C by changing molecular weight of the polymer, polymer concentration, and adding NaCl concentration. The polymers in PBS formed coacervate drops by liquid–liquid phase separations below Tp. Results of the dielectric relaxation measurement, the hydration number per monomeric unit was 5 above Tp. Based on a fluorescence study, the polymer formed slightly hydrophobic environments below Tp. The liquid–liquid phase separation was occurred presumably because of weak hydrophobic interactions and intermolecularly hydrogen bonding interactions between the pendant ureido groups. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2845–2854 相似文献