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1.
In two previous papers (Kinget al., J. Organomet. Chem. 19, 327, 1969; Pannellet al., Organometallics 9, 859, 1990), the synthesis and X-ray structure of the two tetramethyl disilyl complexes [(η5-C5H5) Fe(CO)2]2Si2Me4 (I) and Si2Me4[(η5-C5H4) Fe(CO)2CH3]2 (II) were reported. ComplexII is obtained fromI [2]. However, attempts to form other derivatives fromI have generally failed. In the chemical process to getII fromI, an intermediate complex, Si2Me4[(η5-C5H4) Fe(CO)2] 2 2? (III), is probably formed. This is similar to complexII without the two methyl groups bonded to the Fe atoms. Therefore, a theoretical study that may shed some light on the intermediate structure, stability, and reactivity is justified. We have developed theoretical studies consisting of extended Huckel electronic structure calculations on the simulated intermediate geometry. The results obtained from these calculations suggest that it might be stable enough to form during reactions of complexI. The more reactive sites, which suggest reaction alternatives, are pointed out.  相似文献   

2.
N-Ferrocenoyl glycine ester derivatives FcCONHCH2COOR (Fc=(η5-C5H5)Fe(η5-C5H4); R=methyl (1), ethyl (2) and benzyl (3)) have been prepared by coupling ferrocene carboxylic acid to a series of glycine esters using 1,3-dicyclohexylcarbodiimide (DCC), 1-hydroxybenzotriazole (HOBT) and Et3N in CH2Cl2. The electrochemical anion sensing using a platinum microdisk working electrode of these N-ferrocenoyl glycine ester derivatives is reported. The crystal structure of 1 has been determined; principal dimensions are amide N(H)CO 1.229(3) Å, ester CO 1.183(3) Å with N–H⋯OC(amide) as the primary intermolecular hydrogen bond, N⋯O 2.804(3) Å.  相似文献   

3.
The [Fe2Sb(CO)5Cp]4 (Cp=η5-C5H5) cluster has been obtained by the thermolysis of [Et4N][{Fe(CO)4}2{Fe(CO)2Cp}SbI]. The structure of the [Fe2Sb(CO)5Cp]4·2toluene solvate has been determined by X-ray analysis. The cluster contains the cubane [Fe4Sb4] core. Each Sb serves as a μ4-ligand between three iron atoms of the core and one of a terminal [Fe(CO)2Cp] group.  相似文献   

4.
The synthesis, characterization and X-ray structures of two zirconium complexes of the bulky pentaphenylcyclopentadienyl ligand, CpPRO, are reported. The monocyclopentadienyl 12 electron complex, CpPROZrCl3 (I), has an unusual monomeric structure in the solid state and has short Zr–ligand distances. The Lewis acidity of this complex is manifested in its ability to catalyze the [4+2] cycloadditions of methyl- and ethylmethacrylate to cyclopentadiene. The sandwich complex, CpPROCpZrCl2 (II), has more typical Zr–ligand distances, but has a more parallel arrangement of the two cyclopentadienyl rings.  相似文献   

5.
A one-pot method for the preparation of [Pd{[(η5-C5H3)–CHN–(CH2)2–NMe2]Fe(η5-C5H5)}Cl] is described. Its X-ray crystal structure and its reactions with the diphosphines Ph2P–(CH2)n–PPh2 {with n=1 (ddpm) or 2 (dppe)} are also reported.  相似文献   

6.
Reaction between RhX(PPh3)3 (X = Cl, Br, I) and (η5-C5H4Me)W(CO)3Y (Y = Cl, Br, I) occurs in both the solution and the solid state and leads to exchange of both CO/PPh3 and X/Y between the two reactants.  相似文献   

7.
8.
The reaction of [Os4(CO)9(RCCR)(η6-C6H6)] (R=Me, Ph) with Me3NO in the presence of 1,3-cyclohexadiene or 1,4-cyclohexadiene yields the clusters [{Os4(CO)8(RCCR)(η6-C6H6)}2222-C6H8-1,3)] and [{Os4(CO)8(RCCR)(η6-C6H6)}2222-C6H8-1,4)], respectively. The molecular structure of [{Os4(CO)8(MeCCMe)(η6-C6H6)}2222-C6H8-1,3)] has been determined by single crystal X-ray diffraction, and represents the first example of two osmium cluster fragments linked by 1,3-cyclohexadiene through a μ222-bridge.  相似文献   

9.
10.
A Pd-catalysed Stille coupling of 2,6-diphenyliodobenzene with tributylcyclopentadienyltin gave the sterically constrained ligand precursor cyclopentadienyl-2,6-diphenylbenzene (1). Treatment of this precursor with tetrakis(diethylamido)zirconium(IV) gave the three-legged piano-stool complex [(2,6-Ph2–C6H35-C5H4)Zr(NEt2)3] (2). Complex 2 was characterised by 1H- and 13C{1H}-NMR spectroscopy as well as by X-ray crystallography which showed significant distortions of the three-legged piano-stool geometry as a result of steric interactions with the bulky aryl substituent.  相似文献   

11.
The thermal decomposition of Ru3(CO)10(dppe) in refluxing benzene gives, in contrast to the pyrolysis of the dppm analogue, the tetranuclear cluster Ru4(μ-CO)(CO)944-C6H4)(η214-PCH2CH2PPh2) (1) along with Ru3(CO)9212-C6H5)(η312-PPhCH2CH2PPh2) (2). The single-crystal structure analysis of 1 reveals a square-planar tetraruthenium skeleton containing a η44-benzyne ligand as well as a η214-phosphinidene–phosphine ligand.  相似文献   

12.
13.
A bimetallic 4f–3d tetranuclear complex {[Gd(H2O)4(μ2-C6NO2H5)2Gd(H2O)4](μ3-C6NO2H4)2(ZnCl3)2} · 2H2O · 2Cl (1) has been synthesized via hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Complex 1 is characterized by a tetranuclear Gd2Zn2 structure with the gadolinium and zinc atoms interconnected by isonicotinic acid ligands. The tetranuclear species of {[Gd(H2O)4(μ2-C6NO2H5)2Gd(H2O)4](μ3-C6NO2H4)2(ZnCl3)2} link to isolated chlorine ions and water molecules via π?π interactions and hydrogen bonds to yield a 3-D supramolecular framework. Photoluminescent investigation reveals that the title complex displays an emission in ultraviolet region. The solid-state diffuse reflectance spectra of 1 reveal the presence of a sharp optical gap of 3.66 eV.  相似文献   

14.
The rhenium carbonyl carboxylic acid (η5-C5H4COOH)Re(CO)3 (Re + 1) is readily accesssible in a rapid fashion starting from perrhenate (Re + 7). This complex can be conjugated to amino acids and proteins opening the way to a robust small radiopharmaceutical.  相似文献   

15.
The reaction of dodecacarbonyltriruthenium with tris(2-pyridylmethyl)ammonium perchlorate (tpa·3HClO4), in the presence of acetic acid, afforded a new ruthenium complex of tpa, [Ru(CO)(CH3CO2)(tpa)]ClO4·C6H5CH3 (1). Compound 1 has been characterized by X-ray structural analysis, IR and 1H NMR spectra.  相似文献   

16.
《分离科学与技术》2012,47(6):1338-1364
Abstract

Hydrogen is the energy carrier of the future and could be employed in stationary sources for energy production. Commercial sources of hydrogen are actually operating employing the steam reforming of hydrocarbons, normally methane. Separation of hydrogen from other gases is performed by Pressure Swing Adsorption (PSA) units where recovery of high‐purity hydrogen does not exceed 80%.

In this work we report adsorption equilibrium and kinetics of five pure gases present in off‐gases from steam reforming of methane for hydrogen production (H2, CO2, CH4, CO and N2). Adsorption equilibrium data were collected in activated carbon at 303, 323, and 343 K between 0‐22 bar and was fitted to a Virial isotherm model. Carbon dioxide is the most adsorbed gas followed by methane, carbon monoxide, nitrogen, and hydrogen. This adsorbent is suitable for selective removal of CO2 and CH4. Diffusion of all the gases studied was controlled by micropore resistances. Binary (H2‐CO2) and ternary (H2‐CO2‐CH4) breakthrough curves are also reported to describe the behavior of the mixtures in a fixed‐bed column. With the data reported it is possible to completely design a PSA unit for hydrogen purification from steam reforming natural gas in a wide range of pressures.  相似文献   

17.
Two new 19-vertex metallaboranes, [B18H20Ni(η5-C5H5)][N(CH3)4] and [B18H19(2-THF)Ni(η5-C5H5)], were isolated from the reaction of anti-B18H22 with nickelocene, [Ni(η5-C5H5)2], in high yields. The complexes were characterized by multinuclear NMR (1H, 13C, 11B), IR and UV–vis spectroscopy. Single-crystal X-ray diffraction analyses of these new complexes confirmed their structures as 19-vertex conjuncto-metallaborane clusters.  相似文献   

18.
Reaction of syn-B18H20 with [(η5-C5Me5)IrCl2]2 and base results in multiple metal-centre addition, allied with oxidative cluster closure by multiple dihydrogen loss, giving the twenty-one-vertex globular cluster compound [(η5-C5Me5)3Ir3B18H15(OH)] based on twelve-vertex closo {IrB11} and isonido {Ir2B10} clusters fused with a common five-atom {IrB4} unit that contains a central tetrahedral {IrB3} core.  相似文献   

19.
The reaction of the sodium salt of the monoanion, nido-[2,3-(Si(CH3)3)2-2,3-C2B4H5], with (chloromethyl)dimethylchlorosilane in a 1:1 molar ratio produced the B(cage)-substituted cluster, nido-5-ClCH2Si(CH3)2-2,3-(Si(CH3)3)2-2,3-C2B4H5 (1), in 81% yield. This product (1) was reacted further with the lithium salt of [closo-1-R-1,2-C2B10H10] monoanion (R=Me, Ph) to give the novel linked and mixed C2B4/C2B10 carborane species, 1-Me-2-[5-SiMe2CH2-2,3-(SiMe3)2-2,3-C2B4H5]-1,2-C2B10H10 (2), 1-Ph-2-[5-SiMe2CH2-2,3-(SiMe3)2-2,3-C2B4H5]-1,2-C2B10H10 (3), in yields of 76% and 81%, respectively.  相似文献   

20.
Two new polymeric triorganotin(IV) complexes R3Sn{O2CC6H4[N=C(H)}{C(CH3)CH(CH3)-3-OH]-p} n ([Me3Sn(LH)] n : 1) and ([Ph3Sn(LH)] n : 2) containing a 4-[(2Z)-(3-hydroxy-1-methyl-2-butenylidene)amino]benzoate (LH) framework were prepared. Both compounds have been characterized by 1H, 13C, 119Sn NMR, IR and 119Sn Mössbauer spectroscopic techniques in combination with elemental analyses. The crystal structures of complexes 1 and 2 reveal that they exist as polymeric zig-zag chains in which the LH-bridged Sn-atoms adopt a trans-R3SnO2 trigonal bipyramidal configuration with R groups in the equatorial positions and the axial sites occupied by an oxygen atom from the carboxylate ligand and the alcoholic oxygen atom of the next carboxylate ligand in the chain. The carboxylate ligands coordinate in the zwitterionic form with the alcoholic proton moved to the nearby nitrogen atom.  相似文献   

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