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V. A. Nikanorov A. D. Rogachev M. V. Galakhov T. M. Shcherbina D. V. Zagorevskii V. I. Rozenberg O. A. Reutov V. V. Kaverin V. P. Yur'ev 《Russian Chemical Bulletin》1996,45(2):424-426
The reaction of 2,6-dibenzylidenecyclohexanone with PCl5 occursvia the sequential stages of desoxychlorination and substitutional phosphorylation to form (after oxidation, methoxylation, and hydrolysis on the surface of the chromatographic SiO2 adsorbent) organophosphorus products of the 1-(a-chloro-, a-hydroxy-, or -alkoxy)benzyl-2-chloro-3-(-(dimethylphosphoryl)benzylidene)cyclobex-1-ene series.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 441–443, February, 1996. 相似文献
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V. D. Sviridov N. D. Chkanikov M. V. Galakhov A. F. Kolomiets A. V. Fokin 《Russian Chemical Bulletin》1990,39(4):853-855
Methyl trifluoropyruvate (II) reacts with phenylhydrazine andp-nitrophenylhydrazine to give the corresponding phenylhydrazones (III) and (IV). The reaction of phenylhydrazine with hexafluoroacetone (I) at 20°C leads to the product of the C2-hydroxyalkylation of the aromatic ring (V). The hydroxyalkylation of hydrazobenzene under the same conditions is complicated by a benzidine rearrangement.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 948–950, April, 1990. 相似文献
8.
Andrés R Galakhov MV Gómez-Sal MP Martín A Mena M del Carmen Morales-Varela M Santamaría C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(4):805-811
The photochemical treatment of mu(3)-alkylidyne complexes [[TiCp*(mu-O)](3)(mu(3)-CR)] (R=H (1), Me (2), Cp*=eta(5)-C(5)Me(5)) with the amines (2,6-Me(2)C(6)H(3))NH(2), Et(2)NH, and Ph(2)NH and the imine Ph(2)C=NH leads to the partial hydrogenation of the alkylidyne moiety that is supported on the organometallic oxide, [Ti(3)Cp*O(3)], and the formation of new oxoderivatives [[TiCp*(3)(mu-CHR)(R'NR")] (R"=2,6-Me(2)C(6)H(3), R'=H, R=H (3), Me (4); R'=R"=Et, R=H (5), Me (6); R'=R"=Ph, R=H (7), Me (8)) and [[TiCp*(mu-O)](3)(mu-CHR)(N=CPh(2))] (R=H (9), R=Me (10)), respectively. A sequential transfer hydrogenation process occurs when complex 1 is treated with tBuNH(2), which initially gives the mu-methylene [[TiCp*(mu-O)](3)(mu-CH(2))(HNtBu)] (11) complex and finally, the alkyl derivative [[TiCp*(mu-O)](3)(mu-NtBu)Me] (12). Furthermore, irradiation of solutions of the mu(3)-alkylidyne complexes 1 or 2 in the presence of diamines o-C(6)H(4)(NH(2))(2) and H(2)NCH(2)CH(2)NH(2) (en) affords [[TiCp*(mu-O)](3)(mu(3)-eta(2)-NC(6)H(4)NH)] (13) and [[TiCp*(mu-O)](3)(mu(3)-eta(2)-NC(2)H(4)NH)] (14) by either methane or ethane elimination, respectively. In the reaction of 1 with en, an intermediate complex [[TiCp*(mu-O)](3)(mu-CH(2))(NHCH(2)CH(2)NH(2))] (15) is detected by (1)H NMR spectroscopy. Thermal treatment of the complexes 4-10 quantitatively regenerates the starting mu(3)-alkylidyne compounds and the amine R'(2)NH or the imine Ph(2)C=NH; however, heating of solutions of 3 or 4 in [D(6)]benzene or a equimolecular mixture of both at 170 degrees C produces methane, ethane, or both, and the complex [[TiCp*(mu-O)](3)[mu(3)-eta(2)-NC(6)H(3)(Me)CH(2)]] (16). The molecular structure of 8 has been established by single-crystal X-ray analysis. 相似文献
9.
Abarca A Galakhov MV Gracia J Martín A Mena M Poblet JM Sarasa JP Yélamos C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(10):2337-2346
Treatment of [[Ti(eta(5)-C(5)Me(5))(micro-NH)](3)(micro(3)-N)] (1) with the imido complexes [Ti(NAr)Cl(2)(py)(3)] (Ar=2,4,6-C(6)H(2)Me(3)) and [Ti(NtBu)Cl(2)(py)(3)] in toluene affords the single azatitanocubanes [[Cl(2)(ArN)Ti]( micro(3)-NH)(3)[Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)]].(C(7)H(8)) (2.C(7)H(8)) and [[Cl(2)Ti](micro(3)-N)(2)(micro(3)-NH)[Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)]] (3), respectively. Similar reactions of complex 1 with the niobium and tantalum imido derivatives [[M(NtBu)(NHtBu)Cl(2)(NH(2)tBu)](2)] (M=Nb, Ta) in toluene give the single azaheterometallocubanes [[Cl(2)(tBuN)M](micro(3)-N)(micro(3)-NH)(2)[Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)]] (M=Nb (4), Ta (5)), both complexes react with 2,4,6-trimethylaniline to yield the analogous species [[Cl(2)(ArN)M](micro(3)-N)(micro(3)-NH)(2)[Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)]].(C(7)H(8)) (Ar=2,4,6-C(6)H(2)Me(3), M=Nb (6.C(7)H(8)), Ta (7.C(7)H(8))). Also the azaheterodicubanes [M[micro(3)-N)(2)(micro(3)-NH)](2)[Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)](2)].2C(7)H(8) [M=Ti (8.2C(7)H(8)), Zr (9.2C(7)H(8))], and [M[(micro(3)-N)(5)(micro(3)-NH)][Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)](2)].2 C(7)H(8) (Nb (10.2C(7)H(8)), Ta (11.2C(7)H(8))) were prepared from 1 and the homoleptic dimethylamido complex [M(NMe(2))(x)] (x=4, M=Ti, Zr; x=5, M=Nb, Ta) in toluene at 150 degrees C. X-ray crystal structure determinations were performed for 6 and 10, which revealed a cube- and double-cube-type core, respectively. For complexes 2 and 4-7 we observed and studied by DNMR a rotation or trigonal-twist of the organometallic ligands [[Ti(eta(5)-C(5)Me(5))(micro-NH)](3)(micro(3)-N)] (1) and [(micro(3)-N)(micro(3)-NH)(2)[Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)]](1-). Density functional theory calculations were carried out on model complexes of 2, 3, and 8 to establish and understand their structures. 相似文献
10.
S. D. Chepik V. F. Cherstkov E. I. Mysov A. F. Aérov M. V. Galakhov S. R. Sterlin L. S. German 《Russian Chemical Bulletin》1991,40(11):2285-2291
An unusual electrophilic cyclization of fluorine-containing carbonyl compounds and -oxides was discovered. Upon the action of SbF5, perfluorinated ketones, diketones, and -oxides isomerize to oxolanes. This reaction proceeds with the obligatory participation of the terminal CF3 group.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2611–2618, November, 1991. 相似文献