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1.
Four new complexes of the general formula [Ni(SS)(NN)], Where SSis dddt (5,6-dihydro-1,4-dithiin-2,3-dithiolate) or pddt(6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate) and NNis bpy or phen were prepared. The UV/Vis.Spectra exhibit intense intramolecular ligand-to-ligand charge transfer bands ca.600 nm.Cyclic voltammetry shows a reversible oxidation step assigned to [Ni(SS)(NN)]0=[Ni(SS)(NN)]+. When the complex [Ni(dddt)(bpy)] was partially oxidized by I2, a broad ESRsignal at g=2.003 appeared.  相似文献   

2.
Microsolvation of the [Ni(acac)(tmen)]+ complex by a series of aliphatic n-alcohols (Solv) has been studied in ClCH2CH2Cl solutions by spectrophotometry. Based on the changes in the electronic spectrum of the afore-mentioned complex, observed under the influence of any alcohol, the equilibrium constants for the formation of the [Ni(acac)(tmen)Solv]+ and [Ni(acac)(tmen)Solv2]+ species have been computed according to the algorithm presented in this work. It was found that, in all the systems studied, the stability of five-coordinated [Ni(acac)(tmen)Solv]+ is higher than that of octahedral [Ni(acac)(tmen)Solv2]+. The resulting values are discussed in terms of the Lewis basicity of alcohols.  相似文献   

3.
Two new compounds containing the possible Fe(III) spin-crossover cation, [Fe(qsal)2]+ (qsalH = N-(8-quinolyl)salicylaldimine), and nickel bis(dithiolene) anions have been synthesized. Both are 1 : 1 salts [Fe(qsal)2][Ni(dddt)2] · CH3CN · CH3OH (1) and [Fe(qsal)2][Ni(pddt)2] (2) (dddt = 5,6-dihydro-1,4-dithiin-2,3-dithiolate; pddt = 6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate). They have been characterized by X-ray crystal structure determination, elemental analysis, UV-Vis spectra and magnetic susceptibility measurements. The UV–Vis spectra are dominated by [Ni(L)2]? (1, L = dddt; 2, L = pddt). Magnetic studies show antiferromagnetic interaction in 1 from intermolecular S···S contacts and π–π stacking interactions, while the antiferromagnetic interaction in 2 is very weak.  相似文献   

4.
A nickel metavanadate complex Ni(pz)(V2O6) (pz =?pyrazine) (1) was hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy and thermal analysis. The complex was also investigated by single crystal X-ray diffraction analysis. The three-dimensional extended structure in the crystal is constructed by corner sharing {VO3}n chains running along the b axis and two types of {Ni(pz)}n chains oriented in [0?1?1] and [0?1??1] directions, respectively. Ni is coordinated by two N atoms from two pyrazines and four O atoms from three metavanadates in a distorted octahedral geometry. The variable-temperature magnetic susceptibility of 1 was measured. The magnetic coupling parameter indicates an antiferromagnetic interaction within the {Ni(pz)}n chain.  相似文献   

5.
《中国化学会会志》2017,64(8):925-933
Here we report the density functional calculations of the molecular parameters including the energy, geometries, electric dipole moments, vibrational IR frequencies, and 1H and 13C NMR chemical shifts of Ni(η2‐C6H4 )(H2PCH2CH2PH2 ) (a benzyne complex). Based on the polarizable continuum model (PCM ), the effect of polarity of the solvent on these parameters was explored. The wavenumbers of υ(C1–C2 ) as well as the 1H and 13C NMR chemical shift values of complex in various solvents were calculated and correlated with the Kirkwood–Bauer–Magat equation (KBM ), the solvent acceptor numbers (ANs ), and the linear solvation energy relationship (LSER ). The bonding interaction between the benzyne and Ni(H2PCH2CH2PH2 ) fragment was analyzed by means of the energy decomposition analysis (EDA ). The character of the Ni–C bonds of the molecules was analyzed by natural bond orbital (NBO ) analysis. Also, Monte Carlo simulations were used for the calculation of the total energy and solvation free energy of the complex in water.  相似文献   

6.
A novel 1,2-dithiolate ligand, that is, the 2-(trifluoromethyl)acrylonitrile-1,2-dithiolate, abbreviated here as tfadt, is prepared from the corresponding cyclic dithiocarbonate. This ligand, substituted with both a CN and a CF(3) group, is compared with the well-known maleonitrile- and bis(trifluoromethyl)ethane-1,2-dithiolates. The preparation, electrochemical properties, and X-ray crystal structures of the square-planar nickel complexes, in both their dianionic diamagnetic [Ni(tfadt)(2)](2)(-) and their monoanionic paramagnetic [Ni(tfadt)(2)](*)(-) forms, are reported, as n-Bu(4)N(+), PPh(4)(+), and (18-crown-6)Na(+) salts, respectively. In the [(18-crown-6)Na](2)[Ni(tfadt)(2)] salt, each CN moiety of the [Ni(tfadt)(2)](2)(-) dianion is coordinated to a (18-crown-6)Na(+) cation through a CN...Na interaction [N...Na = 2.481(3) A], affording an "axle with wheels" model where two MeOH molecules act as axle caps. On the other hand, in [(18-crown-6)Na][Ni(tfadt)(2)], each (18-crown-6)Na(+) cation is coordinated on both sides by the CN groups of two monoanionic [Ni(tfadt)(2)](*)(-) complexes with N...Na(+) distances at 2.434(5) and 2.485(4) A, giving rise to heterobimetallic chains with alternating (18-crown-6)Na(+) and [Ni(tfadt)(2)](*)(-) ions. These two examples demonstrate the attractive ability of the CN moieties in the [Ni(tfadt)(2)](2)(-)(,)(*)(-) complexes to coordinate metallic cationic centers. The paramagnetic salts of the anionic [Ni(tfadt)(2)](*)(-) complex follow Curie-type law in the 2-300 K temperature range, indicating the absence of intermolecular magnetic interactions in the solid state. The complexes are found in their trans form in all crystal structures, while density functional theory calculations establish that both forms have essentially the same energy. A cis-trans interconversion process is observed by variable-temperature NMR on the dianionic [Ni(tfadt)(2)](2)(-) complex with a coalescence temperature T(c) of 260 K and a free energy of activation of 51-53 kJ mol(-)(1).  相似文献   

7.
Negishi cross-coupling reaction of organozinc compounds as nucleophiles with aryl halides has drawn immense focus for C−C bond formation reactions. In comparison to the well-established library of Pd complexes, the C−C cross-coupling of this particular approach is largely primitive with nickel-complexes. Herein, we describe the syntheses of Ni(II) complexes, [(MeBICAAC)2NiX2] (X=Cl ( 1 ), Br ( 2 ), and I ( 3 )) by employing the bicyclic (alkyl)(amino)carbene (MeBICAAC) ligand. The reduction of complexes 1 – 3 using KC8 afforded the two coordinate low valent, Ni(0) complex, [(MeBICAAC)2Ni(0)] ( 4 ). Complexes 1 – 4 have been characterized by spectroscopic techniques and their solid-state structures were also confirmed by X-ray crystallography. Furthermore, complexes 1 – 4 have been applied in a direct and convenient method to catalyze the Negishi cross-coupling reaction of various aryl halides with 2,6-difluorophenylzinc bromide or phenylzinc bromide as the coupling partner in the presence of 3 mol % catalyst. Comparatively, among all-pristine complexes, 1 exhibit high catalytic potential to afford value-added C−C coupled products without the use of any additive. The UV-vis studies and HRMS measurements of controlled stochiometric reactions vindicate the involvement of Ni(I)−NI(III) cycle featured with a penta-coordinated Ni(III)-aryl species as the key intermediate for 1 whereas Ni(0)/Ni(II) species are potentially involved in the catalytic cycle of 4 .  相似文献   

8.
《Polyhedron》1999,18(21):2803-2810
Mixed chalcogenide complexes of the type Ni(dppe)(SeC6H4S) (dppe=bis(diphenylphosphino)ethane), Ni(dppe)(SC5H3NCO2) and Ni(dppe)(EC5H3NE′) (E=NH, E′=O; E=E′=NH) have been prepared from the reactions of Ni(dppe)Cl2 with the appropriate aryldichalcogen or pyridine-based compound, using Et3N as a base. The relative solution and thermal stabilities of the above compounds, other mixed chalcogen ones, Ni(dppe)(SC6H4O), Ni(dppe)(SC6H4CO2) and Ni(dppe)(SC6H4NH), and the homoleptic compounds Ni(dppe)(EC6H4E′) (E=E′=O, E=E′=S; R=H, Me), were established by a combination of electron impact mass spectrometry (EIMS) and fast atom bombardment (FABMS). The most stable ones were the compounds with homoleptic sulfur ligands.  相似文献   

9.
Modification of Layer Silicates by Sterically Demanding Metal Complexes: Synthesis and Intercalation of the Square Planar Complexes [Cu(bppep)(H2O)](ClO4)2 and [Ni(bppep)(Cl)]Cl (bppep = 2,6-Bis[1-phenyl-1-(pyridine-2-yl)ethyl]pyridine) in Hectorite Sodium-aqua hectorite reacts with [Cu(bppep)(H2O)](ClO4)2 and [Ni(bppep)(Cl)]Cl with exchange of the sodium-aqua cations against the complex cations [Cu(bppep)(H2O)]2+ and [Ni(bppep)(Cl)]+, respectively. In addition, cation-anion pairs of [Cu(bppep)(H2O)](ClO4)2 and [Ni(bppep)(Cl)]Cl are also intercalated between the hectorite layers (intersalation). On the other hand, it is possible to synthesize [Cu(bppep)(H2O)]2+ or [Ni(bppep)(H2O)]2+ modified hectorites without additional ion-pair intercalation (intersalation) by reaction of nickel- and copper-hectorites with the bppep ligand.  相似文献   

10.
The reaction of H2L (N,N ′-bis(5-ethyl-1,3,4-thiadiazol-2-yl)-2,6-pyridinedicarboxamide) with Ni(II) salts gave crystals of two new complexes, [Ni33-O)(H2L)(L)2] · 2DMF (1) and [Ni2(µ-H2O)(CH3OH)(DMF)(L)2] · H2O · CH3OH (2). The complexes were characterized by elemental analysis, IR, thermal analysis, and X-ray single crystal diffraction. Complex 1 is a trinuclear complex containing a triangle frame in the center formed by three Ni(II) atoms with a bridging µ3-O. Complex 2 is dinuclear formed by two Ni(II) atoms with a bridging H2O. H2L coordinates to metal centers as a pentadentate ligand in 1 and tetradentate in 2. Thermal analysis shows that the thermal stability of 1 is higher than that of 2. In addition, the magnetic properties of 2 are also reported.  相似文献   

11.
From an EtOH/H2O solution, 0.3 M each of Ni2+ and cyclic triamine tacn ( 2 ; tacn=1,4,7‐triazacyclononane), after 10 min refluxing and cooling at room temperature, copious and comparable amounts of blue crystals (containing the complex [Ni(tacn)(H2O)3]2+) and pink crystals (containing in the same cell both [Ni(H2O)6]2+ and [Ni(tacn)2]2+) precipitated. This unusual behaviour is ascribed to the fact that at the refluxing temperature the three species are present at the equilibrium in similar concentrations, which are frozen on cooling, due to the inertness of the macrocyclic complexes [Ni(tacn)(H2O)3]2+ and [Ni(tacn)2]2+.  相似文献   

12.
郭鸿旭  王庆华  陈晨  梁敏  陈铃 《中国化学》2008,26(4):640-644
水热合成并通过红外、热重、单晶X-射线衍射表征了一个新颖镍配位阳离子修饰的还原型钼磷酸盐,Ni[Mo6O12(OH)3(PO4)(HPO4)3]2][Ni(H2O)2][Ni(H2O)(bipy)2]4·5H2O。单晶X-射线衍射研究表明,两个{Mo6P4}簇单元通过一个镍离子连接形成一个Ni[Mo6P4]2二聚结构单元,其进一步和其他的镍配位阳离子连接成钼磷酸盐一维链状结构。在H2O2存在下的液-固体系中,使用该化合物催化氧化苯甲醛的探针反应结果表明,该化合物具有较高的催化氧化活性。  相似文献   

13.
Two polymorphs of monovalent [Ni(dmit)2] (dmit2−=2-thioxo-1,3-dithiole-4,5-dithiolate) crystals A and B, (anilinium)(18-crown-6)[Ni(dmit)2], were prepared, and the structure and magnetic properties were investigated. In these crystals, the [Ni(dmit)2] molecules form dimers, which arranged into chains between the supramolecular cation structure (anilinium)(18-crown-6). In crystal A, supramolecular cation formed a regular stack, inducing ladder structure of [Ni(dmit)2], whose magnetism had been well fitted by spin ladder equation with the spin gap of Δ=190 K. Crystal B is ca. 3% more densely packed compared to crystal A. Due to the dense packing, supramolecular cation stack is distorted, which prevented the intermolecular interaction between [Ni(dmit)2] dimers in direction corresponds to the ladder-leg direction in crystal A. Reflecting the [Ni(dmit)2] arrangement, crystal B showed a temperature dependence of magnetic susceptibility well reproduced by the singlet-triplet thermal activation model, whose antiferromagnetic exchange interaction (2J) was 140 K.  相似文献   

14.
Using non-empirical calculations the details of bonding in Ni(CO)4 and in the analogous Ni(N2)4 are investigated.For Ni(CO)4 some previous results are confirmed. In the calculation on Ni(N2)4 the close resemblance with Ni(CO)4 is quite remarkable. The main difference is contained in the fact that carbon has a lower -electron density than nitrogen and that therefore the *-orbital in CO is lower in energy and geometrically more favourable for back donation.From the calculations we find a difference in metal-ligand bond energy between the carbonyl complex and the dinitrogen complex of approximately 18 kcal/mol.  相似文献   

15.
The anthracycline drug adriamycin and its metal complexes are efficient in treating several forms of human cancers with recognized antineoplastic activity attributed to strong interactions with DNA within the target cells. The hydroxy-9,10-anthraquinone unit present in the molecule controls and regulates drug action. Metal ions when linked to adriamycin help to reduce the generation of radicals responsible for toxic side effects. A complex of adriamycin with Ni(II) was prepared and its physicochemical characteristics and DNA-binding ability were compared to a Ni(II) complex of sodium-1,4-dihydroxy-9,10-anthraquinone-2-sulphonate (NaLH2), an analog of adriamycin. Interactions with calf thymus DNA of both complexes were studied by UV-Vis and fluorescence spectroscopy. Binding parameters determined for both complexes agree with each other. Binding of the Ni(II)-adriamycin complex to DNA was five to eight times stronger than for the Ni(II) complex of the hydroxy-9,10-anthraquinone analog, Na2[Ni(NaLH)2Cl2]?·?2H2O, i.e., Ni(NaLH)2. The difference in binding was attributed to the presence of sugar units in adriamycin and to its absence in NaLH2. Although the Ni(II) complex of the hydroxy-9,10-anthraquinone analog of adriamycin [Ni(NaLH)2] was slightly weaker in binding DNA than the drug and its Ni(II) complex, a much lower cost of the former justifies its consideration as a substitute for the anthracycline drugs that are now in use.  相似文献   

16.
A three‐dimensional polymeric NiII complex, [Ni(bpp)(NIP)(H2O)]n (bpp = 1,3‐di(4‐pyridyl)propane and NIP = 5‐nitroisophthalate), has been synthesized and characterized. The coordination number of the nickel atom is six (NiN2O4) and the coordination environment around the NiII atom may be described as a distorted octahedron in which two nitrogen atoms of “bpp” ligand occupy the cis positions. The effective magnetic moment for this complex indicate that the interactions between two NiII atoms through the effective exchange media are antiferromagnetic. Self‐assembly of these compounds in the solid state via π–π‐stacking interactions is discussed.  相似文献   

17.
The syntheses and crystal structures of four new divalent transition metal complexes of the types [Cu2(dien)2(nic)](ClO4)3 · MeOH (nic = anion of nicotinic acid; dien = diethylenetriamine), 1; [Cu(dien)(nic)]2(nic)2, 2; [Cu(dien)(nic)]2(BF4)2 · 2MeOH, 3 and [Ni(dien)(nic)(H2O)]4(NO3)4 · 2MeOH, 4, are reported, which were prepared by the reactions of diethylenetriamine and nicotinic acid with Cu(ClO4)2 · 6H2O, Cu(OAc)2 · H2O, Cu(BF4)2 · 6H2O and Ni(NO3)2 · 6H2O in MeOH, respectively. These complexes were characterized by single-crystal X-ray diffraction method and elemental analyses. In the cation of complex 1, one nicotinate ligand bridges two Cu(II) metal centers through the pyridyl nitrogen atom and one of the carboxylate oxygen atoms. The cations of complexes 2 and 3 form the twelve-membered metallocycles, involving two Cu(II) ions that are bridged by two nicotinate ligands. The cation of complex 4 forms a tetranuclear cage with the four Ni(II) metal centers bridged by four nicotinate ligands and each Ni(II) metal center adopts the distorted octahedral geometry. Their thermal properties have been investigated by using differential scanning calorimetry (DSC) and thermogravimetric analyses (TGA).  相似文献   

18.
Eight new sulfur-rich [CpCo(dithiolene)] complexes were synthesized from [Zn(dmit)2]2− as a starting material. The structures, electrochemical behavior and electronic absorption spectra of the sulfur-rich [CpCo(S2C2S2Y)] complexes could be compared with the early data of analogous Ni complexes. [CpCo(pddt)] (Y = -(CH2)3-), [CpCo(dpdt)] (Y = -CH2C(CH2)CH2-), [CpCo(bddt)] (Y = -(CH2)4-), [CpCo(dtdt)] (Y = -CH2SCH2-) and [CpCo(poddt)] (Y = -CH2C(O)CH2-) crystallized in all isostructural with the corresponding paramagnetic [CpNi(dithiolene)] complexes, but [CpCo(dmid)] (Y = CO), [CpCo(dddt)] (Y = -(CH2)2-) and [CpCo(F2pddt)] (Y = -CH2CF2CH2-) crystallized in non-isostructural with them. These molecules are associated with intermolecular short S?S contacts in the crystals. [CpCo(F2pddt)] did not show any remarkable S?S contacts but indicated interesting fluorine segregation and Cp?Cp face-to-face interactions. Redox potentials of [CpCo(dithiolene)] complexes were obtained with the cyclic voltammetry measurements and dimerized by electrochemical oxidations. Electronic absorption spectra of [CpCo(dithiolene)] complexes showed visible absorption in the range of 585-701 nm as lowest energy wavelengths (? = 9800-11,800 M−1 cm−1) in solutions, and they were higher energy than those of [CpNi(dithiolene)] complexes (near-IR).  相似文献   

19.
Reaction of Ni(COD)(2) (COD = cyclooctadiene) with dppm (dppm = bis(diphenylphosphino) methane) followed by addition of alkyl or aryl isocyanides yields the class of nickel(0) dimers Ni(2)(mu-CNR)(CNR)(2)(mu-dppm)(2) (R = CH(3) (1), n-C(4)H(9) (2), CH(2)C(6)H(5) (3), i-C(3)H(7) (4), C(6)H(11) (5), t-C(4)H(9) (6), p-IC(6)H(4) (7), 2,6-(CH(3))(2)C(6)H(3) (8)). The cyclic voltammograms of the dimers exhibit two sequential single electron oxidations to the +1 and +2 forms. Specular reflectance infrared spectroelectrochemical (IRSEC) measurements demonstrate reversible interconversions between the neutral Ni(0) dimers and their +1 and +2 forms. Bulk samples of the +2 forms are prepared by chemical oxidation using [FeCp(2)][PF(6)], while the +1 forms are prepared by the comproportionation of neutral and +2 forms. The neutral complexes 6 and 8 were characterized by X-ray diffraction as symmetric, locally tetrahedral binuclear Ni(0) complexes. The +2 forms of these complexes, 6(2+) and 8(2+), have asymmetric structures with one locally square planar and one locally tetrahedral metal center, evidence for a Ni(II)-Ni(0) mixed valence state. The X-ray structural characterization of 6(+) is symmetrical and qualitatively similar to that of the neutral complex 6. The +1 forms all exhibit intense near IR electronic absorptions that are assigned as intervalence charge transfer (IVCT) bands. On the basis of structural, spectroscopic, and electrochemical data, the +1 forms of the complexes, 1(+)-8(+), are assigned as Robin-Day class III, fully delocalized Ni(+0.5)-Ni(+0.5) mixed valence complexes.  相似文献   

20.
The reactivity of superoxide free radicals (O2 · –) generated electrochemically towards the oxydiacetate metal complexes, namely [VO(oda)(H2O)2], [Co(oda)(H2O)2] · H2O, and [Ni(oda)(H2O)3] · 1.5H2O (oda = oxydiacetate) was examined by cyclic voltammetry. The measurements were carried out in DMSO solution using a platinum electrode. Based on the height of the anodic peak Ea that corresponds to electrochemical oxidation O2 · – → O2 + e, in the absence and in the presence of the compounds in the mixture, their O2 · – scavenge ability was assessed. The influence of the type of the complex was briefly discussed. H2O2 was used to induce cellular injury in a mouse hippocampal cell line (HT22). The cytoprotection of chemical compounds was tested at the mitochondrial (MTT test) and plasma membrane level (LDH leakage). Dose‐dependent effect (10 and 100 μM of the complex) of investigated compounds was observed.  相似文献   

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