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1.
A simple and convenient route for synthesizing organotitanium (IV) complexes with a general formula Cp2Ti(SeR)2 or Cp2TiCl(SeR) has been developed. This synthetic route includes reduction of Cp2TiCl2 with Mg and an in situ treatment of the intermediate `Cp2Ti' with diselenides RSeSeR. Interestingly, while the route involving reaction of Cp2TiCl2, Mg and RSeSeR in a molar ratio of 1:1:1 produced Cp2Ti(SeR)2, (1-5, R=α-C10H7, o-MeC6H4, m-MeC6H4, p-ClC6H4, p-BrC6H4) in 91-97% yields, the route involving reaction of Cp2TiCl2, Mg and RSeSeR in a molar ratio of 1: 0.5: 0.5 afforded Cp2TiCl(SeR) (6-7, R=p-ClC6H4, p-BrC6H4) in 70% and 92% yields, respectively. 1-7 are new and have been characterized by elemental analysis and spectroscopy, as well as by X-ray diffraction analysis for 6 and 7. A possible pathway for production of these two types of organotitanium (IV) complexes, mainly depending upon the molar ratio of the starting materials, are briefly discussed.  相似文献   

2.
The new aryl phosphinites PPh2OR (R = 2,4,6-Me3C6H2, 1; R = 2,6-Ph2C6H3, 2) have been prepared from chlorodiphenylphosphine and the corresponding phenols. In these ligands, the ortho-positions of the aromatic phosphite function are blocked by methyl and phenyl substituents, which allows coordination to metal centres without ortho-metallation. Thus, reaction with [PdCl2(cod)] leads to the complexes trans-[PdCl2(PPh2OR)2] (R = 2,4,6-Me3C6H2, 3; R = 2,6-Ph2C6H3, 4), while the reaction with [Rh2(CO)4Cl2] gives trans-[Rh(CO)Cl(PPh2OR)2] (R = 2,4,6-Me3C6H2, 5; R = 2,6-Ph2C6H3, 6). The single-crystal X-ray structure analyses of 3 and 5 confirm the trans-coordination of the new ligands in these square-planar complexes.  相似文献   

3.
The trinuclear arene-ruthenium cluster cation [H3Ru3(C6H6)(C6Me6)2(O)]+, containing a μ3-oxo cap and three arene ligands that span a hydrophobic pocket above the metal skeleton, has been crystallised as tetrafluoroborate salt in the presence of various guest molecules. The host-guest complexes have been characterised by single-crystal X-ray structure analysis. With chloroform as the guest molecule, a CHCl3 molecule sits perfectly in the hydrophobic pocket, the hydrogen atom being encapsulated inside the cavity. When dioxane is added during the crystallisation process, the cluster forms infinite chains which are connected by a complex network of hydrogen bonds involving the μ3-oxo ligand, water and dioxane molecules. Interestingly, in the presence of phenol, a water molecule is hydrogen-bonded between the μ3-oxo ligand and the phenol molecule, forming a one-dimensional μ3-O ? H2O ? HO hydrogen-bonded chain. Finally, with benzoic acid, a head-to-tail host-guest chain is obtained, the phenyl ring being incorporated in the hydrophobic pocket, while the acid group is hydrogen-bonded to the μ3-oxo ligand.  相似文献   

4.
The reaction of lead(II) nitrate with trisodium citrate Na3(C6H5O7) in a 1:22.5 ratio at pH 4.8 provides crystals of {Na(H2O)3}[Pb5(H2O)3(C6H5O7)3(C6H6O7)]·9.5H2O (1). The structure of 1 is two-dimensional and exhibits five distinct Pb(II) sites and four different modes of citrate bonding. The five lead sites all display hemidirected coordination geometries, that is, irregular distribution of neighboring oxygen atoms resulting in obvious gaps in the coordination spheres. Consequently, the lead coordination geometries exhibit proximal bonding to a number of oxygen donors, as well as distal interactions with nearest neighbors. The coordination numbers vary from 8 to 10, with ‘5+3’, ‘5+4’, ‘6+4’ and ‘7+3’ coordination modes where the first number refers to the proximal ligands and the second to the distal set. The four crystallographically distinct citrate groups include three with deprotonated carboxylate groups (C6H5O7)3− and one with a single protonated carboxyl group (C6H6O7)2. The citrate ligands bridge 3, 5, 7 and 7 lead sites. Three of the citrate groups exhibit tridentate chelation coordination to a lead site through two carboxylate oxygen donors and the hydroxyl groups. One citrate group projects an uncoordinated -OH group and a pendant protonated carboxyl group into the interlamellar domain. This latter carboxyl group coordinates to a sodium cation, which exhibits five coordinate geometry defined by three aqua ligands and the carbonyl oxygen of the -CO2H groups in the basal plane and a citrate -OH donor in the apical position.  相似文献   

5.
A new supermolecular assembly crystal, [C6H8N2]6H3[PW12O40]·2H2O (DMB-PWA), was synthesized with phosphotungstic acid (PWA) and 1,2-diaminobenzene (DMB) under hydrothermal conditions and was characterized by Fourier-transform infrared spectra (FTIR) and single-crystal X-ray diffraction analysis. DMB-PWA could effectively catalyze oxidative degradation of chitosan with H2O2 in the heterogeneous phase. The optimum degradation conditions were determined by orthogonal tests as follows: amount of chitosan 1.00 g, 30% (wt %); H2O2, 3.0 mL; dosage of catalyst, 0.06 g; reaction temperature, 85 °C; and reaction time, 30 min. The water-soluble chitosan with a viscosity-average molecular weight (Mv) of 4900 was obtained under the optimum degradation conditions and was characterized by FTIR, ultraviolet-visible diffuse reflection spectra (UV-vis DRS), and X-ray powder diffraction analysis.  相似文献   

6.
A novel organic-inorganic hybrid pentaborate [Ni(C4H10N2)(C2H8N2)2][B5O6(OH)4]2 has been synthesized by hydrothermal reaction and characterized by FT-IR, Raman spectroscopy, elemental analyses and DTA-TGA. Its crystal structure was determined from single crystal X-ray diffraction. The structure consists of isolated polyborate anion [B5O6(OH)4] and nickel complex cation of [Ni(C4H10N2)(C2H8N2)2]2+, in which the two kinds of ligands come from the decomposition of triethylenetriamine material. The [B5O6(OH)4] units are connected to one another through hydrogen bonds, forming a three-dimensional framework with large channel along the a and c axes, in which the templating [Ni(C4H10N2)(C2H8N2)2]2+ cations are located. The assignments of the record FT-IR absorption frequencies and Raman shifts were given.  相似文献   

7.
Short-bite aminobis(phosphonite) containing olefinic functionalities, PhN{P(OC6H3(OMe-o)(C3H5-p))2}2 (1) was synthesized by reacting PhN(PCl2)2 with eugenol in the presence of triethylamine. The ligand 1 acts as a bidentate chelating ligand toward metal complexes [M(CO)4(C5H10NH)2] forming [M(CO)42-PhN{P(OC6H3(OMe-o)(C3H5-p))2}2}] (M = Mo, 2; W, 3). The reaction between 1 and [CpFe(CO)2]2 leads to the cleavage of one of the P-N bonds due to the metal assisted hydrolysis to give a mononuclear complex [CpFe(CO){P(O)(OC6H3(OMe-o)(C3H5-p))2}{PhN(H)(P(OC6H3(OMe-o)(C3H5-p))2)}] (4). Treatment of 1 with gold(I) derivative, [AuCl(SMe2)] resulted in the formation of a dinuclear complex, [(AuCl)2{PhN{P(OC6H3(OMe-o)(C3H5-p))2}2}] (5) with a Au···Au distance of 3.118(2) Å indicating the possibility of aurophilic interactions. An equimolar reaction between 1 and [Ru(η6-p-cymene)Cl2]2 afforded a tri-chloro-bridged bimetallic complex [(η6-p-cymene)Ru(μ-Cl)3Ru{PhN(P(OC6H3(OMe-o)(C3H5-p))2)2}Cl] (6). The crystal structures of 1-3 and 5 were established by single crystal X-ray diffraction studies.  相似文献   

8.
Hydrothermal methods were used to prepare [Cu(O3PC10H6CO2H)] (1) and [Cu(bpy)(HO3PC10H6CO2)]·2H2O (2·2H2O), where H2O3PC10H6CO2H is 2,6-carboxynaphthalene phosphonic acid (H3cnp). The two-dimensional structure of 1 consists of layers of edge-sharing {CuO6} octahedra, producing an AlCl3- type structure of fused hexagonal rings of copper octahedra, enclosing voids of hexagonal profile. The layer composition is CuO3 or CuO6/2 as each oxygen bridges two copper sites. The Hcnp ligands project from either face of the copper “oxide” layer. Adjacent layers interact through hydrogen bonding interactions between the pendant -CO2H groups of the ligand. Coordination of the bipyridine ligand in [Cu(HO3PC10H6CO2)] (2) obstructs expansion in two-dimensions, and the material exhibits a chain structure. The chain is constructed of binuclear units of edge-sharing ‘4+1’ {CuO3N2} square pyramids linked through the dipodal {HO3PC10H6CO2}2− ligands.  相似文献   

9.
The photolytic CO-substitution reaction of the organoiron thiocarboxylate complexes CpFe(CO)2SCOR (R=CH3, 2-CH3C6H4, 2-NO2C6H4, 4-NO2C6H4, 3,5-(NO2)2C6H3) with diphosphines (Ph2P(CH2)nPPh2) [n=1 (dppm), n=2 (dppe), n=3 (dpppr), n=4 (dppb), n=5 (dppp), n=6 (dpph)] at room temperature using 1:2 (metal-ligand) molar ratio afforded exclusively the disubstituted complexes CpFe(Ph2P(CH2)nPPh2)SCOR when n=1, 2 and 3 and the monosubstituted analogs CpFe(CO)(Ph2P(CH2)nPPh2)SCOR when n=4, 5 and 6. This reaction was found to be strongly influenced by the backbone length of the diphosphine ligand, the nature of the R group of the thiocarboxylate moiety and the metal-ligand molar ratios. The crystal structure of CpFe(dppm)SCO(3,5-(NO2)2C6H3) was determined.  相似文献   

10.
The complexes [W(X)Cl3(HO2CC6H4NH-2)] [X = O (1), NPh (2)] have been obtained by reaction of either [WOCl4] or [W(NPh)Cl4(Et2O)] with anthranilic acid {1,2-(NH2)(CO2H)C6H4}, respectively. The X-ray crystal structures reveal pseudo-octahedral metal centres, each with a mer-arrangement of chlorines and a chelating acid/amide ligand derived from anthranilic acid. The acid group of this chelate ligand is trans to either the oxo or organoimido functionality.  相似文献   

11.
A series of palladium complexes of the type [Pd(phPS2)(PAr3)] (phPS2) = [PhP(C6H4-2-S)2]2− have been synthesized in good yields and their crystal structures determined. Heck coupling reactions were carried out using the [Pd(phPS2)(PPh3)] (1), [Pd(phPS2){P(C6H4-4-Cl)3}] (2), [Pd(phPS2){P(C6H4-4-F)3}] (3), [Pd(phPS2){P(C6H4-4-CF3)3}] (4), [Pd(phPS2){P(C6H4-4-Me)3}] (5) and [Pd(phPS2){P(C6H4-4-OMe)3}] (6) complexes as catalyst precursors in order to examine the potential effect of the para-substituted triarylphosphines in the reaction of bromobenzene and styrene.  相似文献   

12.
Two new zincophosphites [C6H14N2]0.5[Zn(H2PO3)2] 1 and [C4H12N2]0.5[(CH3)2NH2][Zn2(HPO3)3] 2 have been solvothermally synthesized in mixed solvents of N,N-dimethylformamide (DMF) and 1,4-dioxane (DOA), respectively. Single-crystal X-ray diffraction analysis reveals that compound 1 exhibits a neutral inorganic chain formed by ZnO4 and HPO2(OH) units. Interestingly, the left- and right-handed hydrogen-bonded helical chains are alternately formed via the hydrogen-bonds between two adjacent chains. Compound 2 exhibits a layer structure with 4- and 12-MRs formed by ZnO4 and HPO3 units, in which two kinds of organic amine molecules both act as countercations to compensate the overall negative electrostatic charge of the anionic network.  相似文献   

13.
New oxovanadium(V) complexes with internally functionalized oximes of the type VO{OPri}3−n{ONC(CH3)(Ar)}n] (where Ar = C4H3O-2, C4H3S-2 and C5H4N-2 and n = 1-3) have been prepared in quantitative yields by the reaction of VO(OPri)3 with the corresponding oximes in various stoichiometric ratios in refluxing anhydrous benzene. The products have been characterized by elemental analyses and spectroscopic (FT IR, 1H, 13C{1H} and 51V NMR) studies. FAB mass spectral analysis of [VO{OPri}{ONC(CH3)C4H3S}2] indicates the monomeric nature of the complex. 51V NMR values for these complexes suggest the formation of tetra-coordinate species in solution. However, the single crystal X-ray diffraction studies of [VO{ONC(CH3)(C4H3O-2)}3] and [VO{ONC(CH3)(C4H3S-2)}3] · 0.5C6H6 exhibit the presence of vanadium(V) atoms in a unique hepta-coordination state with distorted pentagonal bipyramidal geometry in the solid state. The oxo- atom occupies the axial position while the oximato ligands are bonded in a dihapto (η2-N,O) manner with the formation of three membered rings.  相似文献   

14.
The room-temperature electronic spectra of the chromium chalcocarbonyl complexes, Cr(CO)5(CX) and (η6-C6H6)Cr(CO)2(CX) (X = O, S, Se), have been recorded in solution, and in some cases, in the gas phase. Assignments for the thiocarbonyl and selenocarbonyl spectra are proposed on the basis of the literature assignments for the parent all-CO derivatives. Overall, the data support the order of increasing electron withdrawing capacity of the chalcocarbonyl ligands as CO < CS < CSe.  相似文献   

15.
Complexes of Ru(II) containing the pincer ligand [N(2-PPh2-4-Me-C6H3)2] (PNPPh) were prepared. The complex (PNPPhH)RuCl2 (1) was treated with 2 equiv AgOTf to produce the triflate complex (PNPPhH)Ru(OTf)2 (2). Complex 1 was also treated with an excess of NaBH4 to give a bimetallic complex [(PNPPh)RuH3]2 (3). A number of methods, including X-ray crystallography, NMR spectroscopy, and computational studies, were used to probe the structure of 3. Addition of Lewis bases to 3 resulted in octahedral complexes containing a hydride ligand trans to a dihydrogen ligand.  相似文献   

16.
The molecular structure of an o-phenylenediamine unit-containing oligophenylene (1), Ph-Ph′-Ph′(2,3-NH2)-Ph′-Ph (Ph = phenyl; Ph′ = p-phenylene; Ph′(2,3-NH2) = 2,3-diamino-p-phenylene), was determined by X-ray crystallography. 1 has a twisted structure, and forms an intermolecular C-H?π interaction network. The -NH2 group of 1 was air-oxidized to an imine, NH, group in the presence of [RuCl2(bpy)2] (bpy = 2,2′-bipyridyl) and gave a ruthenium(II)-benzoquinone diimine complex [Ru(2)(bpy)2](PF6)2 (2: Ph-Ph′-Ph′(2,3-imine)-Ph′-Ph). The molecular structure of [Ru(2)(bpy)2](PF6)2 was confirmed by X-ray crystallography. [Ru(2)(bpy)2](PF6)2 underwent two-step electrochemical reduction with E1/2 = −0.889 V and −1.531 V versus Fc+/Fc. The E1/2’s were located at higher potentials by 91 mV and 117 mV, respectively, than those of reported [Ru(bqdi)(bpy)2](PF6)2 (bqdi = benzoquinone diimine). Electrochemical oxidation of [Ru(2)(bpy)2](PF6)2 occurred at a lower potential by 180 mV than that of [Ru(bqdi)(bpy)2](PF6)2. Occurrence of the easier reduction and oxidation of [Ru(2)(bpy)2](PF6)2 than those of [Ru(bqdi)(bpy)2](PF6)2 is ascribed to the presence of a large π-conjugation system in 2.  相似文献   

17.
Phosphonium zwitterions of a known type were obtained in high yield via a 1:1 reaction of p-benzoquinone or methoxy-p-benzoquinone with the tertiary phosphines R3P [R = (CH2)3OH, Ph, Et, Me] and Ph2MeP, in acetone or benzene at room temperature. In all cases, attack of the P-atom occurs at a C-atom rather than at an O-atom. The products were characterized to various degrees by elemental analysis, 31P{1H}, 1H and 13C NMR spectroscopies, and mass spectrometry, and two of the zwitterions, the new [HO(CH2)3]3P+C6H2(O)(OH)(MeO) and the known Ph3P+C6H3(O)(OH), were structurally characterized by X-ray analysis. The PEt3 reaction also produces small amounts of the ‘dimeric’, μ-oxo co-product Et3P+C6H2(O)(OH)-O-C6H3(O)P+Et3 that is tentatively characterized by 1D- and 2D-NMR data. 2,5-Di-tert-butyl- and 2,3,5,6-tetramethyl-p-benzoquinone do not react with [HO(CH2)3]3P under the conditions noted above. Heating D2O solutions of the water-soluble zwitterions R3P+C6H3(O)(OH) [R = (CH2)3OH, Et] at 90 °C for 72 h leads to complete H/D exchange of the H-atom in the position ortho to the phosphonium center.  相似文献   

18.
Electron poor cationic complexes [(CF3PCP)Pt(L)]+ (where L = CO, NC5F5, or acetone) react with H2O in polar solvents via selective hydrolysis of a single P-CF3 substituent to afford the spectroscopically-characterized phosphinoyl-bridged complex {k3-P,C,P,k1-O-(CF3)2PCH2C6H3CH2P(CF3)O}2Pt2 (1) in good yield. X-ray diffraction confirms the presence of a six-member Pt-P-O-Pt-P-O ring in a chair conformation. The presumed intermediate aqua complex, (CF3PCP)Pt(H2O)+, is stable in dichloromethane, but when dissolved in more polar solvents readily converts to 1.  相似文献   

19.
The synthesis of new platinum bipy (bipy = 2,2′-bipyridyl) complexes containing phenoxide ligands is reported, together with kinetic studies of their oxidative addition reactions with MeI to produce phenoxo platinum(IV) complexes. Complexes of the form [(bipy)Pt(OC6H4-4-X)2] (X = OCH3, CH3, H, Br, Cl) are prepared by the reaction of the chloro complex [(bipy)PtCl2] with substituted phenols and KOH in a two phase system of water and chloroform in the presence of benzyl triphenylphosphonium chloride. Platinum(IV) complexes are formed by oxidative addition of MeI to the platinum(II) complexes obtained. The complexes are characterized by elemental analysis, UV-Vis, IR, mass spectrometry and 1H and 13C NMR spectroscopy.The reaction of methyl iodide with [(bipy)Pt(OC6H4-4-OMe)2] to give [(bipy)PtMe(I)(OC6H4-4-OMe)2] follows the rate law rate = k2[(bipy)Pt(OC6H4-4-OMe)2][MeI]. The values of k2 increase with increasing polarity of the solvent, suggesting a polar transition state for the reaction.  相似文献   

20.
Two new complexes, {[MnAu2(CN)4(NITpPy)2(H2O)2]}n (1) and {[Co(N(CN)2)2(NITpPy)2(H2O)2]}n (2), have been synthesized and characterized. The single-crystal X-ray analysis for the complexes 1 and 2 demonstrates that each M(II) (M = Mn or Co) ion assumes a distorted octahedral MN4O2 coordination polyhedron. Four nitrogen atoms come from the cyanide groups and the pyridyl rings in a common plane, and two oxygen atoms come from the H2O molecules in trans-positions. The structures of complexes 1 and 2 illustrate that aurophilicity and/or hydrogen bonding interactions play important roles in increasing dimensionality. Magnetic investigations on complexes 1 and 2 show the presence of weak antiferromagnetic interactions.  相似文献   

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