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1.
Ni(II) complexes of [12]aneN4: 1,4,7,10-tetraazacyclododecane-2,3,8,9-tetraone; [14]aneN4: 1,4,8,11-tetraazacyclotetradecane-2,3,9,10-tetraone; Bzo2[12]aneN4: dibenzo-1,4,7,10-tetraazacyclododecane-2,3,8,9-tetraone and Bzo2[14]aneN4: dibenzo-1,4,8,11-tetraazacyclotetradecane-2,3,9,10-tetraone have been encapsulated in the nanopores of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of [bis(diamine)nickel(II)]; [Ni(N–N)2]–NaY; in the supercages of the zeolite, and (ii) in situ condensation of the nickel(II) precursor complex with diethyloxalate. The new host-guest nanocatalyst (HGN) were characterized by several techniques: chemical analysis and spectroscopic methods (FT-IR, UV/Vis, XRD, BET, DRS) and then were used for oxidation of cyclohexene with molecular oxygen.  相似文献   

2.
A series of Co(II) azamacrocyclic complexes, 12 Brunel, D, Bellocq, N, Sutra, P, Cauvel, A, Lasperas, M, Moreau, P, Di Renzo, F, Galarneau, A and Fajula, F. 1998. Coord. Chem. Rev., 178–180: 1085[Crossref], [Web of Science ®] [Google Scholar]aneN4, 14 De Vos, DE, Dams, M, Sels, BF and Jacobs, PA. 2002. Chem. Rev., 102: 3615[Crossref], [PubMed], [Web of Science ®] [Google Scholar]aneN4, Bzo2 12 Brunel, D, Bellocq, N, Sutra, P, Cauvel, A, Lasperas, M, Moreau, P, Di Renzo, F, Galarneau, A and Fajula, F. 1998. Coord. Chem. Rev., 178–180: 1085[Crossref], [Web of Science ®] [Google Scholar]aneN4 and Bzo2 14 De Vos, DE, Dams, M, Sels, BF and Jacobs, PA. 2002. Chem. Rev., 102: 3615[Crossref], [PubMed], [Web of Science ®] [Google Scholar]aneN4, have been encapsulated in the nanocavity of zeolite-Y by a one pot template condensation reaction. Co(II) complexes with azamacrocyclic ligands were entrapped in the nanocavity of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of [bis(diamine)cobalt(II)], [Co(N–N)2]-NaY, in the supercages of the zeolite, and (ii) in situ condensation of the cobalt(II) precursor complex with diethyloxalate. The new host/guest nanocomposite materials (HGNM) have been characterized by FTIR, DRS and UV-Vis spectroscopic techniques, XRD and elemental analysis, as well as nitrogen adsorption. These complexes (neat and HGNM) were used for epoxidation of styrene with O2 as oxidant in different solvents. Electronic spectra of the reaction mixture indicated oxidation proceeds through a free radical mechanism.  相似文献   

3.
Nickel(II) complexes with six co-ordinate tetraoxo dithia tetraaza macrocyclic ligands derived from diamine and which provide a N4S2 co-ordination sphere, [18]aneN4S2: 1,4,10,13-tetraaza-5,9,14,18-tetraoxo-7,16-dithia-cyclooctadecane, [20]aneN4S2: 1,5,11,15-tetraaza-6,10,16,20-tetraoxo-8,18-dithia-cyclocosane, Bzo2[18]aneN4S2: dibenzo-1,4,10,13-tetraaza-5,9,14,18-tetraoxo-7,16-dithia-cyclooctadecane, Bzo2[20]aneN4S2: dibenzo-1,5,11,15-tetraaza-6,10,16,20-tetraoxo-8,18-dithia-cyclocosane, were entrapped in the nanopores of zeolite NaY by a two-step process in the liquid phase: (i) adsorption of [bis(diamine)nickel(II)] (diamine = 1,2-diaminoethane, 1,3-diaminopropane, 1,2-diaminobenzene, 1,3-diaminobenzene); [Ni(N–N)2]2+-NaY; in the nanopores of the zeolite, and (ii) in situ template condensation of the nickel(II) precursor complex with thiodiglycolic acid. The mode of bonding and overall geometry of the complexes and new host/guest nanocomposite materials ([Ni([18]aneN4S2)]2+-NaY, [Ni([20]aneN4S2)]2+-NaY, [Ni(Bzo2[18]aneN4S2)]2+-NaY, [Ni(Bzo2[20]aneN4S2)2+-NaY) has been inferred through FT-IR, DRS and UV–vis spectroscopic techniques, molar conductance and magnetic moment data, XRD and elemental analysis, as well as nitrogen adsorption. An octahedral geometry around the nickel(II) ion is suggested for the complexes and new host/guest nanocomposite materials.  相似文献   

4.
This work reports the synthesis and characterization of macrocyclic copper(II) complexes encapsulated within the nanopores of zeolite-Y. The obtained nanoparticles entrapped in the nanopores of zeolite have been characterized by FT-IR, UV–Vis, Diffuse reflectance spectra, spectroscopic techniques, molar conductance, magnetic moment data, XRD, thermal, and elemental analysis. The complexes (neat and encapsulated) were used for the oxidation of cyclooctene with tert-butyl hydroperoxide as oxidant in different solvents. The supported Cu[L1]2+-Y exhibited a moderate 81.9% selectivity for epoxidation with 84.2% conversion. The catalytic activity and selectivity of the heterogeneous catalysts do not change after recycling five times.  相似文献   

5.
Masoud Salavati-Niasari   《Polyhedron》2008,27(14):3132-3140
Ni(II) complexes of [14]aneN4: 1,5,8,12-tetraaza-2,9-dioxo-4,11-diphenylcyclotetradecane; [16]aneN4: 1,5,9,13-tetraaza-2,10-dioxo-4,12-diphenylcyclohexadecane; Bzo2[14]aneN4: dibenzo-1,5,8,12-tetraaza-2,9-dioxo-4,11-diphenylcyclotetradecane and Bzo2[16]aneN4: dibenzo-1,5,9,13-tetraaza-2,10-dioxo-4,12-diphenylcyclohexadecane have been encapsulated in the nanopores of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of [bis(diamine)nickel(II)] (diamine = 1,2-diaminoethane, 1,3-diaminopropane, 1,2-diaminobenzene, 1,3-diaminobenzene); [Ni(N–N)2]2+–NaY; in the nanopores of the zeolite-Y, and (ii) in situ condensation of the nickel(II) precursor complex with ethylcinnamate. The new host–guest nanocomposite materials (HGNM) were characterized by several techniques: chemical analysis and spectroscopic methods (FT-IR, UV/Vis, XRD and DRS) and the BET technique. These complexes were used for oxidation of cyclohexene with molecular oxygen.  相似文献   

6.
Ce(IV) salophen encapsulated into dealuminated Y zeolite was prepared by the flexible ligand method. Incorporation of TiO2 into nanocages of dealuminated Y zeolite was performed by the impregnation method. The obtained photocatalyst was characterized by FT-IR, XRD, DRS, SEM, EDS and ICP techniques. The amount of Ce(salophen) in the zeolite supercages was 0.07 mg/g of encapsulated zeolite. This catalytic system was investigated in the photodegradation of 4-nitrophenol. In this work, the effect of dark conditions, and visible and UV illumination was investigated for the degradation of 4-nitrophenol. In addition, the effect of other parameters including catalyst loading, H2O2 and TiO2 was studied in the degradation of 4-nitrophenol. The obtained results reveal that the photocatalyst performance depends on catalyst loading, the presence of H2O2, and UV illumination.  相似文献   

7.
A series of Co(II) tetraoxodithiatetraaza macrocyclic complexes ([18]aneN4S2, [20]aneN4S2, Bzo2[18]aneN4S2 and Bzo2[20]aneN4S2) have been encapsulated in the nanopores of zeolite Y by template condensation reaction. Co(II) complexes with tetraoxodithiatetraaza macrocyclic ligand were entrapped in the nanopores of zeolite Y by a two-steps process in the liquid phase: (i) ion-exchange of [bis(diamine)cobalt(II)] (diamine = 1,2-diaminoethane, 1,3-diaminopropane, 1,2-diaminobenzene, 1,3-diaminobenzene); [Co(N–N)2]2+–NaY; in the nano-cavity of the zeolite, and (ii) in situ template condensation of the cobalt(II) precursor complex with thiodiglycolic acid. The mode of bonding and overall geometry of the complexes and new host/guest nanocomposite materials ([Co([18]aneN4S2)]2+–NaY, [Co([20]aneN4S2)]2+–NaY, [Co(Bzo2[18]aneN4S2)]2+–NaY, [Co(Bzo2[20]aneN4S2)2+–NaY) has been inferred through FT-IR, DRS and UV–Vis spectroscopic techniques, BET technique, molar conductance and magnetic moment data, XRD and elemental analysis, as well as nitrogen adsorption. The average number of encapsulated Co complexes per nano-cavity was determined to be 0.33 for the Co complexes–NaY. An octahedral geometry around the cobalt(II) ion is suggested for the complexes and new host/guest nanocomposite materials.  相似文献   

8.
In the present work, a mild and efficient method has been developed for the synthesis of acylals from aldehydes with acetic anhydride in the presence of molybdophosphoric acid encapsulated into dealuminated zeolite Y (MPA-DAZY) as a catalyst under solvent-free conditions at 45–55 °C in good to excellent yield. The deprotection of acylals has also been attained using this catalyst in acetonitrile. The catalyst was reused several times without efficient loss of its catalytic activity.  相似文献   

9.
Reaction of HgSO4 with one molar equivalent of L{L = [18]aneN2S4 (1,4,10,13-tetrathia-7,16-diazacyclooctadecane) or Me2[18]aneN2S4 (7,16-dimethyl-1,4,10,13-tetrathia-7,16-diazacyclooctadecane)} in refluxing MeOH-H2O for 15 min affords a colourless solution containing the complex cation [Hg(L)]2+. Addition of excess PF6 counterion gives the complex [Hg([18]aneN2S4)](PF6)2·4/3H2O as a cream coloured solid. A single crystal X-ray structure determination shows mercury(II) bound to a severely distorted octahedral arrangement of the six macrocyclic donor atoms, Hg---S = 2.655(5), 2.735(4), 2.751(4), 2.639(5) Å, Hg---N = 2.473(11), 2.472(17) Å. The cation is in a rac configuration with the two SCH2CH2NCH2CH2S linkages bound meridionally to the metal centre.  相似文献   

10.
Mn(II) complexes of 12-membered macrocyclic ligands with three different donating atom sets (N2O2, N2S2 and N4) in the macrocyclic ring have been encapsulated in the nanopores of zeolite-Y by the Flexible-Ligand Method (FLM). The complexes were entrapped in the nanocavity of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of 1,2-di(o-aminophenyl-, amino, oxo, thio)ethane in the supercages of the zeolite and (ii) in situ condensation of the Mn(II) precursor complex ([Mn(N2X2)]2+) with glyoxal or biacetyl. The new host–guest nanocatalysts, [Mn([R]2–N2X2)]2+–NaY (R = H, CH3; X = NH, O, S), have been characterized by various physico-chemical methods. These complexes, both in their free states and as host–guest nanocatalysts, were used for oxidation of cyclohexene with tert-butylhydroperoxide (TBHP) oxidant in different solvents. Di-2-cyclohexenylether was identified as the main product. 2-Cyclohexene-1-one, 2-cyclohexene-1-ol and 1-(tert-butylperoxy)-2-cyclohexene were obtained as minor products. [Mn([H]2–N4)]2+–NaY was found to give the best reactivity and selectivity.  相似文献   

11.
In order to gain information about the coordinating properties of the chelating ligands Me2XGeMe2(CH2)2X′Me2 (abbr. XGeCCX′) the chemical and spectroscopic results obtained during the synthesis of the M(CO)4(XGeCCX′) complexes (M = Cr, Mo, W; X, X′ = N, P, As) are critically discussed and compared with the results for the analogous five-membered ring chelates M(CO)4(KGeCX′).  相似文献   

12.
Cu(II) complexes of 14- and 16-membered tetraaza macrocyclic ligands have been encapsulated in nanopores of zeolite-Y by a two-step process in the liquid phase: (1) adsorption of [bis(diamine)copper(II)] (diamine = 1,2-diaminoethane, 1,3-diaminopropane, 1,2-diaminobenzene, and 1,3-diaminobenzene); [Cu(N–N)2]2+–NaY; in the nanopores of the zeolite-Y and (2) in situ condensation of the copper(II) precursor complex with ethylcinnamate. The new host–guest nanocomposite materials were characterized by chemical analysis and spectroscopic methods. The “neat” and encapsulated complexes exhibit good catalytic activity in the oxidation of ethylbenzene at 333 K, using tert-butyl hydroperoxide as the oxidant. Acetophenone was the major product though small amounts of o- and p-hydroxyacetophenones were also formed revealing that C–H bond activation takes place both at benzylic and aromatic ring carbon atoms.  相似文献   

13.
用高效液相色谱(HPLC)法测定了水溶液中碱催化下异构体-(差向立体异构体):Δ(S)∧(R)和Δ(R)∧(S)-[Co(tp)2(Me3-en)]ClO4(tp:2-羟基-2,4,6-环庚三烯-1-酮负离子;Me3-en:N,N,N'-三甲基乙二胺)手性配位氮的翻转(差向立体异构体)速率常数kep(34.0 ℃),研究结果发现,碱催化下手性配位氮的翻转作用具有二级反应动力学方程:v=kep[配合物][OH^-],[Co(tp)2(Me3-en)]ClO4的kep值比[Co(tp)2(Me3-en)]ClO4的kep值大一个数量级,Δ(R)∧(S)-异构体比Δ(S)∧(R)-异构体具有更大的手性配位氮翻转速率。  相似文献   

14.
The thermally (decomp. temp. 300°C) and completely air stable, novel coordination polymers [(Me3SnIV)2(Me3SbV)MII(CN)6] with M = Fe and Ru can be prepared by co-precipitation from aqueous solutions of Me3SnCl, Me3SbBr2 and K4[(M(CN)6], or, alternatively, by the ion-exchange-like reaction of the polymers [A(Me3Sn)3M(CN)6] (A+ = Et4N+, Cp2Co+, Me3Sn+ etc.) with Me3SbBr2. IR-spectroscopic findings suggest a statistical distribution of quasi-octahedral M(CN-Sn··)6-x(CNSb ··)x building blocks (with x = 0–6) within a three-dimensional network.  相似文献   

15.
Well-crystallized cobalt and nickel hydrogencyanamide, Co(HNCN)2 and Ni(HNCN)2, were synthesized from the corresponding ammonia complexes [M(NH3)6]2+ under aqueous cyanamide conditions. The X-ray and neutron powder data evidence the orthorhombic system and space group Pnnm. The cell parameters for Co(HNCN)2 are a=6.572(1), b=8.805(2), c=3.267(1) Å, and Z=2; for the isotypic Ni(HNCN)2, the cell parameters arrive at a=6.457(1), b=8.768(2), c=3.230(1) Å. The octahedral coordinations of the metal ions are marginally squeezed, with interatomic distances of 4×Co-N=2.134(5) Å, 2×Co-N=2.122(9) Å, and 4×Ni-N=2.133(6) Å, 2×Ni-N=2.035(11) Å. The HNCN units appear as slightly bent (177.5(2)° for Co(HNCN)2 and 175.7(2)° for Ni(HNCN)2) and exhibit cyanamide shape character due to triple- and single-bond C-N distances (1.20(2) vs. 1.33(2) Å for Co(HNCN)2 and 1.15(2) vs. 1.38(2) Å for Ni(HNCN)2). The infrared vibration data compare well with those of the three existing alkali-metal hydrogencyanamides.  相似文献   

16.
Employing 3-dimethylamino-1-propylamine as a template, a new three-dimensional (3-D) zincophosphite (C5H16N2)·[Zn3(HPO3)4]·H2O has been prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction (XRD), FTIR, elemental analysis, powder XRD, and thermogravimetric analysis (TGA). The compound crystallizes in the triclinic space group , with cell parameters, a=8.9884(2) Å, b=10.326(2) Å, c=11.917(2) Å, α=66.98(3)°, β=89.01(3)°, and γ=78.98(3)°, V=997.2(3) Å3 and Z=2. The connectivity of the ZnO4 tetrahedra and HPO3 pseudo pyramids results in inifinite edge-sharing, ladderlike chains of 4-membered rings, which are further linked by Zn-O-P bonds to form a 3-D structure that with interesting 12-membered ring channels along the [100] and [001] directions. The diprotonated amine molecules sit in the middle of the channels along the [100] direction and interact with the framework via hydrogen bonds. There also exist channels with 8-membered ring window along the [100] and [010] directions.  相似文献   

17.
Single crystals of KxMg(8+x)/3Sb(16−x)/3O16 (x≈1.76) with a hollandite superstructure were grown. Ordering schemes for guest ions (K) and the host structure were confirmed by the structure refinement using X-ray diffraction intensities. The space group is I4/m and cell parameters are a=10.3256(6), c=9.2526(17)Å with Z=3. Superlattice formation is primarily attributed to the Mg/Sb occupational modulation in the host structure. Mg/Sb ratios at two nonequivalent metal sites are 0.8977/0.1023 and 0.1612/0.8388. Two types of the cavity are seen in the tunnel, where parts of K ions deviate from the cavity center along the tunnel direction. Probability densities for K ions in the two cavities are different from each other, which seems to have arisen from the Mg/Sb modulation.  相似文献   

18.
[2-(Me2NCH2)C6H4]HgCl (1) was prepared by reacting HgCl2 with [2-(Me2NCH2)C6H4]Li in diethyl ether. The reactions of 1 with the sodium or ammonium salt of the appropriate thiophosphinato ligand, in 1:1 molar ratio, afford the isolation of [2-(Me2NCH2)C6H4]Hg[S(S)PR2] [R=Me (2), Et (3), Ph (4)], [2-(Me2NCH2)C6H4]Hg[S(O)PPh2] (5) and [2-(Me2NCH2)C6H4]Hg[S(S)P(OiPr)2] (6). The compounds were investigated by IR and multinuclear NMR (1H, 13C and 31P) spectroscopy. The molecular structures of 1 and 4 were determined by single-crystal X-ray diffraction. Due to the strong intramolecular coordination of the N atom of the pendant CH2NMe2 arm [Hg(1)-N(1) 2.764(6) and 2.725(4) Å in 1 and 4, respectively] both compounds exhibit a T-shaped (C,N)HgX core in the molecular unit, with almost linear arrangement of the covalent bonds [C(1)-Hg(1)-Cl(1) 176.93(18)° in 1, and C(1)-Hg(1)-S(1) 169.54(16)° in 4]. The crystals of 1 contain discrete monomeric molecules, while the crystals of 4 contain dimer associations built through asymmetric bridging dithiophosphinato ligands [Hg(1)-S(1) 2.3911(16) Å, Hg(1)?S(2a) 3.102(2) Å], thus resulting in an overall pseudo-trigonal bipyramidal (or seesaw) (C,N)HgS2 core, with the nitrogen atom and the weekly bonded sulfur atom in equatorial positions [N(1)-Hg(1)?S(2a) 82.01(10)°].  相似文献   

19.
《Comptes Rendus Chimie》2017,20(5):520-525
Zeolite Y was dealuminated by chemical methods (with ethylenediaminetetraacetic acid) to modify the zeolite structure for 12-molybdophosphoric acid (MPA) loading. MPA was encapsulated in the nanocavities of modified dealuminated zeolite Y (MDAZY) and characterized by Fourier transform infrared, X-ray diffraction, and atomic absorption spectroscopy. The new catalyst was applied for an efficient chemoselective synthesis of tetrahydrobenzo[b]pyran derivatives, and the corresponding products were obtained in good to excellent yields in very short reaction times. Furthermore, the catalytic activity of this new catalyst in the synthesis of tetrahydrobenzo[b]pyrans was compared with MPA encapsulated in zeolite Y dealuminated by the hydrothermal method. The catalyst (MPA–MDAZY) was recovered and reused several times without loss of its catalytic activity.  相似文献   

20.
The reactions of lanthanide tris(borohydrides) Ln(BH4)3(thf)3 (Ln = Sm or Nd) with 2 equiv. of lithium N,N′-diisopropyl-N′-bis(trimethylsilyl)guanidinate in toluene produced the [(Me3Si)2NC(NPri)2]Ln(BH4)2Li(thf)2 complexes (Ln = Sm or Nd), which were isolated in 57 and 42% yields, respectively, by recrystallization from hexane. X-ray diffraction experiments and NMR and IR spectroscopic studies demonstrated that the reactions afford monomeric ate complexes, in which the lanthanide and lithium atoms are linked to each other by two bridging borohydride groups. The complexes exhibit catalytic activity in polymerization of methyl methacrylate. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 441–445, March, 2007.  相似文献   

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