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101.
K. Nakatsu Y. Inai T. Mitsudo Y. Watanabe H. Nakanishi Y. Takegami 《Journal of organometallic chemistry》1978,159(1):111-122
The crystal structure of a bis(triphenylphosphine)iminium salt of the 1:1 adduct of [FeH(CO)4]? and dimethyl acetylenecarboxylate has been determined from three-dimensional X-ray data collected by the counter method. Single crystals belong to the triclinic space space group P, with two units of [C36H30NP2]+[C10H7FeO8]? in a cell of dimensions: = 13.918(2), = 15.669(5), = 9.909(2) Å, = 91.22(3), = 94.83(2), and = 77.62(2)°. The structure was refined to a conventional of 0.068 for 5373 observed reflections. The resulting structure indicates that the complex anion is η3-[-2,3-bis(methoxycarbonyl)acryloyl]tricarbonylferrate, the coordination around the iron atom being described as a considerably distorted trigonal bipyramid. A comparison of the present structure with the structures of related complexes suggests that the η3-acryloyl portion is best represented as an intermediate of (η3-allyl) with the oxygen atom and (η2-olefin + η1-acyl). The short Fe-C(acyl) length of 1.897(5) Å implies an enhanced back-donation of electrons from the iron atom to the acyl group. 相似文献
102.
Mitsudo Ishikawa Hiroshi Sugisawa Keiji Yamamoto Makoto Kumada 《Journal of organometallic chemistry》1979,179(4):377-390
The photolysis of six ethynyl-substituted polysilanes has been investigated in the presence or absence of methanol. Irradiation of 1-ethynyl-2-phenyl- and 1-ethynyl-1-phenyltetramethyldisilane (I and II), 1-ethynyl-1,1-diphenyltrimethyldisilane (III) and 2-ethynylheptamethyltrisilane (V) in the presence of methanol produced methoxysilanes arising from the corresponding reactive silacyclopropene and silapropadiene intermediates. Irradiation of 1-enthynylheptamethyltrisilane (IV) led to the formation of dimethylsilylene, ethynylpentamethyldisilane and 1,1-dimethyl-2-pentamethyldisilanyl-1-silacyclopropene intermediate. The photolysis of tris(trimethylsilyl)ethynylsilane (VI) in the presence of methanol produced 1-trimethylsilyl-1-bis(trimethylsilyl)methoxysilylethene and hexamethyldisilane. Photolysis of II and III in the absence of a trapping agent gave the respective bis(silyl)acetylenes, via a 1,2-hydrogen shift, from the transient silacyclopropenes, in moderate yields, whereas the yields of the rearranged acetylenes from IV and V were low. 相似文献
103.
H. Hoshizuki S. Mitsudo T. Saji K. Matsuura T. Idehara M. Glyavin A. Eremeev T. Honda Y. Iwai H. Nishi A. Kitano J. Ishibashi 《International Journal of Infrared and Millimeter Waves》2005,26(11):1531-1541
Boron carbide (B4C) is one of advanced materials and is being used in a wide rage of applications. The unique feature of this material is its
large neutron-absorbing cross-section. Some of its most prominent applications are controlling rods in nuclear reactors and
radiation protection. 24 GHz microwave processing for B4C ceramics were performed under flowing argon gas using the sintering system. Sintering at the high temperature (up to 2200°C)
was achieved using thermal insulation system consists of fiber-board, boron nitride powder, and boron nitride case. The sintered
samples were achieved 90 % of theoretical. 相似文献
104.
K Itami T Nokami Y Ishimura K Mitsudo T Kamei J Yoshida 《Journal of the American Chemical Society》2001,123(47):11577-11585
A novel strategy for the diversity-oriented synthesis of multisubstituted olefins, where 2-pyridyldimethyl(vinyl)silane functions as a versatile platform for olefin synthesis, is described. The palladium-catalyzed Heck-type coupling of 2-pyridyldimethyl(vinyl)silanes with organic iodides took place in the presence of Pd2(dba)3/tri-2-furylphosphine catalyst to give beta-substituted vinylsilanes in excellent yields. The Heck-type coupling occurred even with alpha- and beta-substituted 2-pyridyldimethyl(vinyl)silanes. The one-pot double Heck coupling of 2-pyridyldimethyl(vinyl)silane took place with two different aryl iodides to afford beta,beta-diarylated vinylsilanes in good yields. The palladium-catalyzed Hiyama-type coupling of 2-pyridyldimethyl(vinyl)silane with organic halides took place in the presence of tetrabutylammonium fluoride to give di- and trisubstituted olefins in high yields. The sequential integration of Heck-type (or double Heck) coupling and Hiyama-type coupling produced the multisubstituted olefins in regioselective, stereoselective, and diversity-oriented fashions. Especially, the one-pot sequential Heck/Hiyama coupling reaction provides an extremely facile entry into a diverse range of stereodefined multisubstituted olefins. Mechanistic considerations of both Heck-type and Hiyama-type coupling reactions are also described. 相似文献
105.
106.
107.
La Agusu T. Idehara H. Mori T. Saito I. Ogawa S. Mitsudo 《International Journal of Infrared and Millimeter Waves》2007,28(5):315-328
Design of a CW 1 THz gyrotron at second harmonic operation using a 20 T superconducting magnet has been described. The mode
competition analysis is employed to investigate operation conditions of second harmonic mode, which is being excited at the
frequency ranging from 920 GHz to 1014 GHz. The output power up to 250 watt corresponding to the efficiency of 4.16 percent
could be achieved by using an electron beam with accelerating voltage 30 kV and current 200 mA. The important advantage of
this gyrotron is that the single mode excitation at second harmonic, and extremely high frequency of the radiation, could
be maintained even at high currents. It opens possibility to realize a high power radiation source at 1 THz. Such gyrotron
is under construction at FIR Center, University of Fukui. 相似文献
108.
109.
Metal-catalyzed hydrosilylation of alkenes and alkynes using dimethyl(pyridyl)silane is described. The hydrosilylation of alkenes using dimethyl(2-pyridyl)silane (2-PyMe(2)SiH) proceeded well in the presence of a catalytic amount of RhCl(PPh(3))(3) with virtually complete regioselectivity. By taking advantage of the phase tag property of the 2-PyMe(2)Si group, hydrosilylation products were isolated in greater than 95% purity by simple acid-base extraction. Strategic catalyst recovery was also demonstrated. The hydrosilylation of alkynes using 2-PyMe(2)SiH proceeded with a Pt(CH(2)=CHSiMe(2))(2)O/P(t-Bu)(3) catalyst to give alkenyldimethyl(2-pyridyl)silanes in good yield with high regioselectivity. A reactivity comparison of 2-PyMe(2)SiH with other related hydrosilanes (3-PyMe(2)SiH, 4-PyMe(2)SiH, and PhMe(2)SiH) was also performed. In the rhodium-catalyzed reaction, the reactivity order of hydrosilane was 2-PyMe(2)SiH > 3-PyMe(2)SiH, 4-PyMe(2)SiH, PhMe(2)SiH, indicating a huge rate acceleration with 2-PyMe(2)SiH. In the platinum-catalyzed reaction, the reactivity order of hydrosilane was PhMe(2)SiH, 3-PyMe(2)SiH > 4-PyMe(2)SiH > 2-PyMe(2)SiH, indicating a rate deceleration with 2-PyMe(2)SiH and 4-PyMe(2)SiH. It seems that these reactivity differences stem primarily from the governance of two different mechanisms (Chalk-Harrod and modified Chalk-Harrod mechanisms). From the observed reactivity order, coordination and electronic effects of dimethyl(pyridyl)silanes have been implicated. 相似文献
110.
The reaction of diphenylketene with terminal acetylenes catalyzed by tetrakis-(triphenylphosphine)palladium gave disubstituted acetylenes in high yields. 相似文献