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1.
The reactions of Zn(NO 3) 2 · 6H 2O and FeSO 4 · 7H 2O with 4-PDS (4-PDS = 4,4′-dipyridyldisulfide) and NH 4SCN in CH 3OH afforded the complexes [Zn(NCS) 2(4-PDS)] n (1) and [Fe(NCS) 2(4-PDS) 2 · 4H 2O] n (2), respectively, while the reaction of CoCl 2 · 6H 2O with 4-PDS in CH 3OH gave the complex {[Co(4-PDS) 2][Cl] 2 · 2CH 3OH} n, (3). These complexes have been characterized by spectroscopic methods and their structures determined by X-ray crystallography. The 4-PDS ligands in 1 are coordinated to the metal centers through the nitrogen atoms to form 1-D zigzag-chains, and the distorted tetrahedral coordination geometry at each zinc center is completed by a pair of N-bonded thiocyanate ligands. Compound 2 has a 1-D channel-chain structure and each octahedral Fe(II) metal center is coordinated by four 4-PDS ligands and two trans N-bonded thiocyanate ligands. Weak SS interactions in complex 1 link the 1-D chains into 2-D molecular sheets. In complex 2, the channel chains are interlinked through SS interactions to form molecular sheets, which interpenetrate through the SS interactions to form 3-D structures with large cavities that are occupied by the water molecules. Compound 3 also has a 1-D channel-chain structure with each square-planar Co(II) metal center coordinated by four 4-PDS ligands. Multiple C–HCl hydrogen bonds and SO interactions in 3 link the 1-D chains into 2-D structures. 相似文献
2.
Three interpenetrated polymeric networks, {[Co(bpp)(OH-BDC)] · H 2O} n (1) [Ni(bpp) 1.5(H 2O)(OH-BDC)] n (2) and {[Cd(bpp)(H 2O)(OH-BDC)] · 2H 2O} n (3), have been prepared by hydrothermal reactions of 1,3-bis(4-pyridyl)propane (bpp), 5-hydroxyisophthalic acid (OH-H 2BDC), with Co(NO 3) 2 · 6H 2O, Ni(NO 3) 2 · 6H 2O and Cd(NO 3) 2 · 4H 2O, respectively. Single-crystal X-ray diffraction analyses reveal that the three compounds all exhibit interpenetrated but entirely different structures. Compound 1 is a fourfold interpenetrated adamantanoid structure with water molecules as space fillers, in which bpp adopts a TG conformation ( T = trans, G = gauche). Compound 2 is an interdigitated structure from the interpenetrated long arms of one-dimensional molecular ladders, while bpp in 2 adopts both TT and TG conformations. Compound 3 is a twofold interpenetrated three-dimensional network from a one-dimensional metal-carboxylate chain bridged by TG conformational bpp. The hydrogen bonding interactions in 1–3 further stabilize the whole structural frameworks and play critical roles in their constructions. 相似文献
3.
When the polymeric complex [Ag(im)] n (Him = imidazole) is reacted with PPh 3 (PPh 3 = triphenylphosphine), it yields the [Ag 2(μ 2-im) 2(PPh 3) 3] n and [Ag(μ 2-im)(PPh 3) 2] n species, shown to contain wavy chains of metal ions, singly bridged by N, N′- exo-bidentate imidazolate ligands. The former, crystallised as the CH 2Cl 2 solvate, contains two non-equivalent silver(I) ions, differing in the number of coordinated phosphines (one, in trigonal planar stereochemistry, or two, having tetrahedral geometry). The latter has a unique independent silver(I) ion in a tetrahedral environment, with two coordinated PPh 3 ligands. The reactivity of known silver(I) azolates with PPh 3, as well as the solution behaviour and (when available) the crystal structures of the corresponding derivatives are taken into consideration for a due comparison. 相似文献
4.
Synthesized hydrated lamellar acidic crystalline magadiite (H 2Si 14O 29·2H 2O) nanocompound was used as host for intercalation of polar n-alkylmonoamine molecules of the general formula H 3C(CH 2) nNH 2 ( n = 1–6) in aqueous solution. The original interlayer distance ( d) of 1500 pm, determined by X-ray powder diffraction patterns, increases after intercalation. The values correlated with the number of aliphatic amine carbon ( nc) atoms: d = [(1312 ± 11) + (21 ± 2)] nc. The amount of intercalated amines ( Ns), decreased as nc increased: Ns = [(5.82 ± 0.04) − (0.45 ± 0.01)] nc. The acidic layered nanocompound was calorimetrically titrated with the amines and the thermodynamic data gave exothermic values for all guest molecules, as shown by the correlation: Δ intH = −[(24.45 ± 0.49) − (1.91 ± 0.10)] nc and d = [(1576 ± 16) − (10.8 ± 1.0)]Δ intH. The negative values of the Gibbs energies and the positive entropies also presented the correlations: Δ intG = −[(22.8 ± 0.2) − (0.2 ± 0.1)] nc and Δ intS = [(6 ± 1) + (5 ± 1)] nc, respectively. 相似文献
5.
Reaction between 5,5′-methylenebis(salicylaldehyde) or 5,5′-dithiobis(salicylaldehyde) and 1,2-diaminocyclohexane in equimolar ratio leads to the formation of new polymeric chelating ligands [–CH 2(H 2sal-dach)–] n (I) and [–S 2(H 2sal-dach) 2–] n (II). These ligands react with [VO(acac) 2] in DMF to give coordination polymers [–CH 2{VO(sal-dach)·DMF}–] n (1) and [–S 2{VO(sal-dach)·DMF}–] n (2). Both complexes are insoluble in common solvents and exhibit a magnetic moment value of 1.74 and 1.78 μB, respectively. IR spectral studies confirm the coordination of ligands through the azomethine nitrogen and the phenolic oxygen atoms to the vanadium. These complexes exhibit good catalytic activity towards the oxidation of styrene, cyclohexene and trans-stilbene using tert-butylhydroperoxide as an oxidant. Concentration of the oxidant and reaction temperature has been optimised for the maximum oxidation of these substrates. Under the optimised conditions, oxidation of styrene gave a maximum of 76% (with 1) or 85% (with 2) conversion having following products in order of selectivity: benzaldehyde > styreneoxide > 1-phenylethane-1,2-diol > benzoic acid. A maximum of 98% conversion of cyclohexene was obtained with both the catalysts where selectivity of cyclohexeneoxide varied in the order: 2 (62%) > 1 (45%). With the conversion of 33% (with 1) and 47% (with 2), oxidation of trans-stilbene gives benzaldehyde, benzil and trans-stilbeneoxide as major products. 相似文献
6.
The phosphorus azide [P(O 2C 12H 8)(N 3)] [(O 2C 12H 8) = 2,2′-dioxy-1,1′-biphenyl] undergoes a solid state polymerization at 30 °C giving a separable mixture of the polyphosphazene {[NP(O 2C 12H 8)]} n with a Mw in the range of 10 4, together with a fraction of small and large cyclic spirophosphazene oligomers {[NP(O 2C 12H 8)]} n, and an insoluble polymeric material with a very high char forming tendency, consisting very likely on a network of large interlooped cyclic oligomers and polymers of overall composition [NP(O 2C 12H 8)] n. The reaction proceeds with smooth though irregular release of nitrogen at first but tending to abrupt accelerations ending in an explosion. The later outcome is more likely in scales of 10–50 g, and results in a decrease in the yield of the soluble polymer and a large increase in the yield of the polymeric matrix. 相似文献
7.
A photoluminescent supramolecular compound [Cd(Hbic) 2(H 2O)]·(4,4′-bpy)·H 2O, H 2bic = 1-H-benzimidazole-5-carboxylic acid, has been synthesized and structurally characterized. With CH–π stacking and hydrogen bond, the 4,4′-bipyridine is used as template to construct the neighboring layers into a three-dimensional supramolecular architecture. Solid-state emission spectrum of compound 1 shows luminescence with emission peak at 565 nm. 相似文献
8.
The reactions of BrMn(CO) 5 with the non-chelating stereochemically rigid bidentate ligands (L-L) 1,3-, and 1,4-diisocyanobenzene, 4,4′-diisocyanobiphenyl, and 4,4′-diisocyanodiphenylmethane afford well characterized complexes of the types BrMn(CO) 4(L-L), BrMn(CO) 3(L-L) 2, and [BrMn(CO) 4] 2(L-L). Similar reactions with [RC 5H 4Mn(CO) 2NO] +PF 6− gave mixtures of oligomers of the type [(RC 5H 4MnNO) n(L-L) n+1] n+[PF 6−] n. 相似文献
9.
Three novel uranyl complexes with organic phosphine oxide ligands and bridging fluorides have been synthesised and structurally characterised. In [ UO 2(μ-F)(TPPO) 3 2][BF 4] 2 · nC 6H 14, 1, and [ UO 2(-μF)(TBPO) 3 2][BF 4] 2 2, (where TPPO and TBPO are triphenylphosphine oxide and tri- n-butylphosphine oxide, respectively) two UO 2 2+ moieties are bridged by two fluorides with three additional terminal PO donor ligands coordinated to each uranium centre. The dicationic complexes are both charge balanced by two uncoordinated tetrafluoroborate anions. In the related structure, [UO 2(μ-F)(F)(DPPMO 2)] 2 · 2MeOH (3), terminal fluoride is also coordinated to both uranyl centres (where DPPMO 2 = bis(diphenylphosphine oxide)methane). All three complexes were prepared during attempted syntheses of complexes with tetrafluoroborate directly coordinated to uranium. It is clear from these results that the fluorophilicity of UO 2 2+ causes the abstraction of fluoride from [BF 4] −, with the weakly coordinating anion only present as a counter cation in 1 and 2, and absent completely in 3. 相似文献
10.
Reactions of Co 3(μ 3-CBr)(μ-dppm)(CO) 7 with {Au[P(tol) 3]} 2{μ-(CC) n} ( n=2–4) have given {Co 3(μ-dppm)(CO) 7}{μ 3:μ 3-C(CC) nC} [ n=2 (1), 3 (2), 4 (3)] containing carbon chains capped by the cobalt clusters. Tetracyanoethene reacts with 2 to give {Co 3(μ-dppm)(CO) 7} 2{μ 3:μ 3-C(CC) 2C[=C(CN) 2]C[=C(CN) 2]C} (4). X-ray structural characterisation of 1, 3 and 4 are reported, that for 3 being the first of a cluster-capped C 10 chain. 相似文献
11.
The structures of 3,3′-dicarbometoxy-2,2′-bipyridine ( dcmbpy) complexes with copper(II) and silver(I) cations have been determined using single crystal X-ray-diffraction. The crystals of Cu( dcmbpy)Cl 2 are monoclinic, C2/ c, a = 16.966(3), b = 18.373(3), c = 13.154(2) Å, β = 126.543(3)°. The crystals of Ag( dcmbpy)NO 3 · H 2O are also monoclinic, C2/ c, a = 16.7547(13), b = 11.0922(9), c = 18.7789(18) Å, β = 100.228(7)°. The results have been compared with the literature data on the complexes of dcmbpy and its precursors: 2,2′-bipyridine ( bpy) and 3,3′-dicarboxy-2,2′-bipyridine ( dcbpy). Two types of complexes of 3,3′-carboxy derivatives of bpy are distinguished: (1) with metal atom bonded to two N atoms of the same molecule and (2) with metal atom bonded to two N atoms of two different molecules. The Cu( dcmbpy)Cl 2 complex belongs to the first type, whereas Ag( dcmbpy)NO 3 · H 2O belongs to the second type. 相似文献
12.
Lewis acid/base addition between Ln(NO 3) 3 · 6H 2O (Ln = Pr, Nd, Sm, Eu, Tb and Lu) and H 2salen [H 2salen = N, N′-ethylenebis(salicylideneimine)] gives rise to an array of coordination polymeric structures. Crystal structural analysis reveals that Salen effectively functions as a bridging ligand in these compounds. The size of the lanthanide ions controls the structures of these Salen lanthanide complexes. Two representative structures with one dimensional and two dimensional topologies, viz. [Pr(H 2salen)(NO 3) 3(CH 3OH) 2] n (1) and [Ln(H 2salen) 1.5(NO 3) 3] n [Ln = Pr (2), Nd (3), Sm (4), Eu (5), Tb (6) and Lu (7)] are reported. Luminescent spectra of complexes 4 and 5 exhibit characteristic metal-centered emission lines. However, the characteristic luminescence of the terbium(III) ion is not observed either in solution or in the solid state of complex 6. 相似文献
13.
139La-NMR chemical shifts were measured for several anionic complexes of formulae Li(C 4H 8O 2) 3/2 [La(ν 3-C 3H 5) 4], [Li(C 4H 8O 2) 2][Cp′ nLa(ν 3-C 3]H 5) 4−n] (Cp′ = Cp(ν 5-C 5H 5); n = 1, 2 and Cp′ = Cp * (ν 5-C 5Me5); N = 1) and Li[R nLa(ν 3-C 3H 4) 4− n] (R = N(SiMe 3) 2; n = 1, 2 and R = CCsIMe 3; n = 4), as well as for neutral compounds for formulae La(ν 3-C 3H 5) 3L n (L = (C 4H 8O 2) 1.5, (HMPT) 2, TMED), Cp′ nLa(ν 3-C 3H 5) 3−n (Cp′= Cp(ν 5-Cp 5H 5), Cp *(ν 5-C 5Me 5); n = 1, 2) and La(ν 3-C 3H 2) 2X(THF) 2 X = Cl, Br, I). Typical ranges of the 139La-NMR chemical shifts were found for the different types of complex independent of number and kind of organyl groups directly bonded to lanthanum. Zusammenfassung139La-NMR-Spektroskopie wurde an einer Reihe anionischer Allyllanthanat(III)-Komplexe der Zusammensetzung
]- [La)ν3-C3H5)4, [Li(C4H8)2][Cp′nLa(ν3-C3H5)4−n(Cp′ = Cp(ν5-C5H5); n = 1, 2 und Cp′ = Cp * (ν5-C5Me5); N = 1) und Li[RnLa(ν3-C3H5)4−n (R = B(SiMe3)2; n = 1, 2 und R = CCSiMe3; n = 4 sowie neutraler Allyllanthan(III)-Komplexe der Zusammensetzung La(ν3-C3H5)3Ln (Ln = (C4H8O2)1.5, (HMPT)2, TMED), Cp′n, La(ν3-C3H5)3−n (Cp′ = Cp(ν5-C5H5), Cp * (ν5- Cp5Me5); n = 1, 2) und La(ν3-Cp3H5)2X(THF)2 (X = Cl, Br, I) durchgefürt. In Abhängikeit von der Anzahl und der Art der am Lanthan gebundenen Gruppen wurden für die verschieden Komplextypen charakteristische Resonanzbereiche ermittelt. 相似文献
14.
Three new complexes {[Cu(dpdapt)(Hhbd)] · 6H 2O} n (1) (dpdapt = N, N′-di(2-pyridyl)-2,4-diamino-6-phenyl-1,3,5-triazine, Hhbd = 2-hydroxybutanedioicate dianion), [Cu(dpdapt)(SO 4)] · 2H 2O (2) and [Cu(dpdapt)(oxa)] · H 2O (3) (oxa = oxalate dianion) have been synthesized and structurally characterized. The non-covalent interactions of π–π stacking and hydrogen bonding extend complexes 1–3 into supramolecular architectures, where 1 self-assembles into a 1D polymeric chain by dicarboxylate bridges and exhibits a 3D framework with 1D open channels, while complexes 2 and 3 display 2D wavelike networks. Interestingly, in 1, the host framework encapsulates hexameric water clusters that are connected into 1D arrays by supramolecular association along the 1D open channels. The UV/vis, IR spectra, fluorescence and TG analysis for complexes 1, 2 and 3 are also discussed. 相似文献
15.
Two polymeric complexes, [Cu 2(btec)(phen) 2] n·(H 2O) n (1) and [Cd 4(btec) 2(phen) 4(H 2O) 4] n (2) (H 4btec=1,2,4,5-benzenetetracarboxylic acid; PHEN=1,10-phenanthroline), were synthesized by solvothermal reactions at 140 °C. Both complex 1 and 2 possess infinite double-chain structures, in which each Cu(II) center has a tetrahedral configuration and the Cd(II) centers adopt triangular prismatic and square-based pyramidal configurations simultaneously. The inter-chain face to face π–π interactions among the aromatic rings of phen and the hydrogen bond interactions between aqua molecules and carboxyl O atoms result in 3-D networks in the two complexes. The ESR spectra study of complex 1 shows that there is negligibly small long-range super-exchange interactions between the Cu(II) atoms via benzenecarboxylate bridging. 相似文献
16.
The title cobalt(III) complexes have been investigated by polarized absorption and Raman spectroscopies of the single crystals. The symmetry properties of the d-electron orbitals and of the vibrational modes attributable to the Raman bands of trans(Cl 2)-[CoCl 2(NH 3) n(H 2O) 4−n]Cl complexes ( n = 2, 3, or 4) were examined to elucidated the peculiar observation that ligand substitution causes no splitting of the 15 200-cm −1 absorption band and the 250-cm −1 Raman band. Effects of replacing the NH 3 ligand with H 2O on the electronic structure, atom–atom force constants and vibrational modes of these complex ions are briefly described. 相似文献
17.
We have calculated the optimized structures and stabilization energies for hydrated clusters of orthoboric acid molecule, B(OH) 3(H 2O) n ( n=1–5), with a hybrid density functional approach. Although some ion-pair structures are revealed in the case of n=4 and 5 clusters, the most stable structure is found to be a non-proton-transferred form up to n=5 hydrated clusters. The calculated IR spectra of the stable B(OH) 3(H 2O) n of n=3–5 clusters predict small red shifts of hydrogen-bonded OH frequencies. These geometry and IR results are related to the weak acidity nature of orthoboric acid. 相似文献
18.
The synthesis and reactivity of {(η 5-C 5H 4SiMe 3) 2Ti(CCSiMe 3) 2} MCl 2 (M = Fe: 3a; M = Co: 3b; M = Ni: 3c) is described. The complexes 3 are accessible by the reaction of (η 5-C 5H 4SiMe 3) 2Ti(CSiMe 3) 2 (1) with equimolar amounts of MCl 2 (2) (M = Fe, Co, Ni). 3a reacts with the organic chelat ligands 2,2′-dipyridyl (dipy) (4a) or 1,10-phenanthroline (phen) (4b) in THF at 25°C to afford in quantitative yields (η 5-C 5H 4SiMe 3) 2Ti(CSiMe 3) 2 (1) and [Fe(dipy) 2]Cl 2 (5a) or [Fe(phen) 2]Cl 2 (5b). 1/ n[Cu IHal] n (6) or 1/ n[Ag IHal] n (7) (Hal = Cl, Br) react with {(η 5 -C 5H 4SiMe 3) 2Ti(CCSiMe 3) 2}FeCl 2 (3a), by replacement of the FeCl 2 building block in 3a, to yield the compounds {(η 5-C 5H 4SiMe 3) 2Ti(C CSiMe 3) 2}Cu IHal (8) or {(η 5-C 5H 4SiMe 3) 2Ti(CSiMe 3) 2}Ag IHal (9) (Hal = Cl, Br), respectively. In 8 and 9 each of the two Me 3SiCC-units is η 2-coordinated to monomeric Cu I Hal or Ag IHal moieties. Compounds 8 and 9 can also be synthesized by the reaction of (η 5-C 5H 4SiMe 3) 2 Ti(CSiMe 3) 2 (1) with 1/ n[Cu IHal] n (6) or 1/ n [Ag IHal] n (7) in excellent yields. All new compounds have been characterized by analytical and spectroscopic data (IR, 1H-NMR, MS). The magnetic moments of compounds 3 were measured. 相似文献
19.
A series of novel heterobimetallic crown ether-like polyoxadiphosphaplatinaferrocenophanes cis-[1,1′-Fc(CH 2O(CH 2CH 2O) nCH 2CH 2PPh 2) 2]PtCl 2 ( n=1–3) (4a–c) was synthesized in good yield by cyclization of the bis(phosphine) ligands 1,1′-Fc(CH 2O(CH 2CH 2O) nCH 2CH 2PPh 2) 2 ( n=1–3) (3a–c) and (PhCN) 2PtCl 2 under high dilution conditions in CH 2Cl 2. The bisphosphines 3a–c are obtained by reaction of the corresponding diols 1,1′-Fc(CH 2O(CH 2CH 2O) nCH 2CH 2OH) 2 ( n=1–3) (1a–c) with: (i) CH 3SO 2Cl in CH 2Cl 2 and (ii) LiPPh 2 in THF. Although the X-ray crystal structure of 4a shows that the cavity is large enough for the encapsulation of small metal cations, inclusion experiments of 4a–c with Group 1 cations, and Mg 2+, or NH 4+ in solution applying NMR titration and cyclovoltammetric methods reveal no evidence for the formation of host–guest complexes for 4a,b. In the case of 4c only the addition of Na + or K + leads to an insignificant effect. 相似文献
20.
The coordination of 1,5-bis-(1′-phenyl-3′-methyl-5′-pyrazolone-4′)-1,5-pentanedione (BPMPPD) and 2,2′-bipyridine (bipy) with lanthanide ions in water-alcohol solution has been studied. Binuclear complexes of the types : Ln 2(BPMPPD) 3(bipy) 2· nH 2O ( n = 2 for Y, n = 4 for Eu, Gd, Dy, Ho, Er, Tm and Yb); Ln 2(BPMPPD) 3bipy· nH 2O ( n = 10 for La, n = 3 for Pr, Nd, Sm and Tb) were formed. The compounds were characterized by elemental analysis, molar conductance, IR, UV, 1H NMR spectroscopy, thermogravimetric analysis and fluorescence spectra. 相似文献
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