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71.
Liang-Fu Tang Wen-Li JiaZhi-Hong Wang Ji-Tao WangHong-Gen Wang 《Journal of organometallic chemistry》2002,649(2):152-160
The reaction of 3(5)-methylthio-5(3)-phenylpyrazole with dibromomethane under phase-transfer catalytic conditions only affords a new ligand, bis(3-phenyl-5-methylthiopyrazol-1-yl)methane. However, the reaction of 3(5)-methylthio-5(3)-p-methoxyphenylpyrazole or 3(5)-methylthio-5(3)-tert-butylpyrazole with dibromomethane under the same conditions yields three isomers, respectively, indicating that the substituents significantly affect the steric and electronic properties of pyrazole ring during the formation of ligands. Treatment of these potential polydentate ligands with M(CO)6 (M=Cr, Mo or W) under UV irradiation at room temperature affords (NN)M(CO)4 derivatives, in which some complexes contain asymmetric substituted bis(pyrazol-1-yl)methane ligands. The X-ray crystal structure analyses indicate that the sulfur atoms in these complexes do not take part in the coordination to the metal centers, and S-rich bis(pyrazol-1-yl)methanes actually act as bidentate chelating ligands by two nitrogen atoms. It is also interesting that in order to reduce the repulsion of methyl groups with carbonyls, the methyl groups in these complexes are oriented away from the metal centers. 相似文献
72.
73.
Brunner H Cattey H Meier W Mugnier Y Stückl AC Wachter J Wanninger R Zabel M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(16):3796-3802
The reaction of the cluster salts [Cp(2*) Nb(CO)(2)](n)[Co(11)Te(7)(CO)(10)] (Cp*=C(5)Me(5); n=1, 2) with excess PMe(2)Ph gave the neutral, dark brown clusters [Co(11)Te(7)(CO)(6)(PMe(2)Ph)(4)] (5) and [Co(11)Te(7)(CO)(5)(PMe(2)Ph)(5)] (6) with 147 metal valence electrons. The new compounds were characterized by IR spectroscopy, elemental analyses, and mass spectrometry. The molecular structure of 6 was determined by X-ray crystallography. Like its precursor anion, it consists of a pentagonal-prismatic [Co(11)Te(7)] core, but with a ligand sphere composed of five CO and five PMe(2)Ph ligands. Detailed electrochemical studies of both reactions reveal that a stepwise substitution of CO ligands in the initial cluster anions takes place leading to intermediate [Co(11)Te(7)(CO)(10-m)(PMe(2)Ph)(m)](n-) ions (m=1-5; n=1, 2). Each of these intermediates is distinguished by at least one oxidation and two reduction waves, giving rise to a total of 21 redox couples and 27 electroactive species. The electron sponge character of the new compounds is particularly pronounced in 5, which exhibits charges n between +1 and -4 corresponding to metal valence electron counts of between 146 and 151. 相似文献
74.
Ulrich Schubert 《Journal of Sol-Gel Science and Technology》2003,26(1-3):47-55
Organically substituted metal alkoxides can be prepared by reaction of the parent alkoxides with complexing organic compounds. The chemical and structural consequences of such substitutions are discussed in this article. Examples are given showing how functional organic moieties, such as polymerizable groups, can be incorporated into sol-gel materials via the complexing ligands. Major structural differences between silica-based and metal-based hybrid materials originate from the different charge/coordination number ratios of silicon and most metals. This results in a high tendency for the molecular building blocks to aggregate. In many cases, metal oxide clusters are formed which are capped by the organic ligands. Such surface-modified clusters are themselves very valuable condensed matter units for materials syntheses. 相似文献
75.
Fonseca GS Umpierre AP Fichtner PF Teixeira SR Dupont J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(14):3263-3269
Stable transition-metal nanoparticles of the type [M(0)](n) are easily accessible through the reduction of Ir(I) or Rh(III) compounds dissolved in "dry" 1-n-butyl-3-methylimidazolium hexafluorophosphate ionic liquid by molecular hydrogen. The formation of these [M(0)](n) nanoparticles is straightforward; they are prepared in dry ionic liquid whereas the presence of the water causes the partial decomposition of ionic liquid with the formation of phosphates, HF and transition-metal fluorides. Transmission electron microscopy (TEM) observations and X-ray diffraction analysis (XRD) show the formation of [Ir(0)](n) and [Rh(0)](n) nanoparticles with 2.0-2.5 nm in diameter. The isolated [M(0)](n) nanoparticles can be redispersed in the ionic liquid, in acetone or used in solventless conditions for the liquid-liquid biphasic, homogeneous or heterogeneous hydrogenation of arenes under mild reaction conditions (75 degrees C and 4 atm). The recovered iridium nanoparticles can be reused several times without any significant loss in catalytic activity. Unprecedented total turnover numbers (TTO) of 3509 in 32 h, for arene hydrogenation by nanoparticles catalysts, have been achieved in the reduction of benzene by the [Ir(0)](n) in solventless conditions. Contrarily, the recovered Rh(0) nanoparticles show significant agglomeration into large particles with a loss of catalytic activity. The hydrogenation of arenes containing functional groups, such as anisole, by the [Ir(0)](n) nanoparticles occurs with concomitant hydrogenolysis of the C-O bond, suggesting that these nanoparticles behave as "heterogeneous catalysts" rather than "homogeneous catalysts". 相似文献
76.
铂锡双金属催化剂上丙烷脱氢反应研究 总被引:2,自引:0,他引:2
对比研究了Sn/Pt比为1;1,2,:1和5:1的原子簇担载于γ-Al2O3上制成的Pt=Sn原子簇催化剂,和用SnCl2和H2PtCl6浸渍制备的相应Sn/Pt比的催化剂对丙烷脱氢生成丙烯的催化性能。 相似文献
77.
N. A. Ustynyuk M. G. Peterleitner O. V. Gusev L. I. Denisovich 《Russian Chemical Bulletin》1993,42(10):1727-1730
The electrochemical behavior of rhodium sandwich complexes containing η4-pentamethylcyclopentadiene or tetramethylfulvene fragments has been studied by cyclic voltammetry. The complexes undergo
one-electron oxidation to give unstable 17-electron radical cations which are converted into rhodocenium salts as a result
of elimination or uptake of hydrogen or C-C bond cleavage.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1802–1805, October, 1993. 相似文献
78.
报道了用H_2Fe(CO)_4制备trans-Fe(CO)_3(PR_3)_2的新的羰基取代反应。在 过量质子存在下,H_2Fe(CO)_4中的羰基被活化,中心铁原子对膦的亲核进攻更为 敏感。在这种条件下H_2Fe(CO)_4与膦反应时,首先失去氢生成Fe(CO)_4(PR_3), Fe(CO)_4-(PR_3)再与第二个膦反应可高产率的得到trans-Fe(CO)_3(PR_3)_2。用 PPh_3与Fe(CO)_4(PPh_3)在过量质子存在下反应生成trans-Fe(CO)_3(PR_3)_2,证 实了上述过程。 相似文献
79.
超声波作用下羰基化合物的还原偶联反应 总被引:5,自引:0,他引:5
超声波在一些有机反应中有明显的促进作用「“,Luche等认为超声波的作用有两种主要类型[’j.一类是涉及电子转移的自由基或离子一自由基型反应,由于超声波的空化作用所产生的局部高温高压可以促进电子转移,从而明显地加快反应速度;对大多数离子型反应,超声波只能起到机械的物理作用.我们曾报道偕二卤化合物在Li、Na、Mg等金属作用下产生卡宾的反应是单电子转移过程,该反应可由于超声辐射而大大加速[‘];而在芳基叔脚的断裂反应中,超声波可以促进三苯基俄与金属馊反应生成二苯基脚负离子,但对它进一步的亲核取代反应却没有明… 相似文献
80.
本文利用高压法制备HFe2Co(CO)9(μ3-S),作为原料,经脱质子化作用,再分别与(PPh3)2Cu(NO3)和PPh3AuCl反应,将Ph3Cu-或Ph3Au-联接到原始簇合物的中心骨架上,使簇核扩大,得到了组成为(PPh3)2CuFe2Co(CO)8(μ3-S)和(PPh3)3AuFe2Co(CO)7(μ3-S)的化合物.文中对此两个新化合物进行了IR,UV,1H和31P NMR.元素分析、熔点测定等性质表征,并对(PPh3)2CuFe2Co(CO)7(μ3-S)进行了单晶X-射线衍射分析.两个化合物具有类似的中心骨架,在Fe2和Co原子三角形的上面和下面分别键联着Cu和S,或Au和S原子,构成了三角双锥结构.其中一个簇合物由二个三苯基膦和八个羰基配位,另一个则由三个三苯基膦和七个羰基配位. 相似文献