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1.
The crystal and molecular structures of the organomercury(II) complexes [Hg(C6H5)(chtsc)], 1, and [Hg(C6H5C5H4N)(btsc)], 2, obtained from the reaction of phenylmercury(II) acetate with cyclohexanone thiosemicarbazone (Hchtsc) and that of [2-(pyridin-2′-yl)]phenyl]mercury(II) acetate with benzaldehyde thiosemicarbazone (Hbtsc), respectively, are described. Both 1 and 2 are monoclinic, space group C2/c. Complex 1 has a distorted T-shaped geometry {C-Hg-S, 161.91(10)°} and 2 can be considered to have a distorted seesaw geometry {C-Hg-S, 171.2(10)°}. In both complexes the ligands act as bidentate chelating anions bonding through azomethine N1 and thiolato S atoms.  相似文献   

2.
Summary Using cyclohexanone thiosemicarbazone as ligand (L), nickel(II) complexes, NiL2X2 · nH2O, have been prepared for various anions. Their properties are as follows: X = Cl, green paramagnetic, 5-coordinate; X = Br dimorphous; green, diamagnetic, square-red; paramagnetic, possibly square pyramidyl; X = nitrate, dimorphous-anhydrous, red, diamagnetic, planar; dihydrated, green, paramagnetic, traps-octahedral; X = acetate, intermediate; X = thiocyanate, paramagnetic, parrot green, isothiocyanate, octahedral, X = sulphate, dimorphous anhydrous, brown, diamagnetic. planar; trihydrate, blue, diamagnetic and planar.  相似文献   

3.
Hydrogen bonds of phenol–cyclohexanone and phenol–H2O2 in the studied Baeyer–Villiger (B–V) oxidation have been investigated by HF, B3LYP, and MP2 methods with various basis sets. The accurate single‐point energies were performed using CCSD(T)/6‐31+G(d,p) and CCSD(T)/aug‐cc‐pVDZ on the optimized geometries of MP2/6‐31+G(d,p). It has been confirmed that B3LYP/6‐31+G(d,p) could be used to study such hydrogen bonds. Energetic analysis of complexes was carried out using the Xantheas method with BSSE corrected by CP method. Orbital energy order (ε) illuminated that phenol with good hydrogen donor‐acceptor property can interact with cyclohexanone or H2O2 to form hydrogen bound complexes, and the binding energies (BE) range from ?4.38 to ?14.06 kcal mol?1. NBO analysis indicated that the redistribution of atomic charges in the complexes facilitated nucleophilic attack of H2O2 on cyclohexanone. The calculated results match remarkably well with the experimental phenomena. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009  相似文献   

4.
采用固定床模式,研究了钛硅分子筛催化环己酮制环己酮肟液相氨肟化反应.结果表明,该工艺模式具有可行性与普适性.优化的反应条件为:温度333K,体系氨浓度>2%,酮/H2O2摩尔比=5,H2O2空速0.083h-1.此时环己酮转化率、环己酮肟选择性、H2O2转化率及其有效利用率分别达18.7%,99.5%,94.7%和98.7%.进一步研究了H2O2在该过程中的反应行为,发现固定床工艺模式能有效提高H2O2的有效利用率,其主要原因是该模式有利于羟胺的生成及其进一步与酮反应生成肟.适当的空速与氨和酮的浓度是实现H2O2高效利用的关键因素.  相似文献   

5.
A cyclohexanone solution of H2PtCl6 was examined to find the catalytic species responsible for the hydrosilylation of the olefinic C=C bond. Similarly to other H2PtCl6–solvent systems (e.g. Speier's and Karstedt's catalysts), the real catalyst appeared to be colloidal platinum formed in situ by stepwise reduction [Pt(IV)→Pt(O)] and dechlorination of the platinum precursor. The role of cyclohexanone seems to be to form sufficiently stable platinum complexes to avoid rapid platinum precipitation and aggregation. The studies of H2PtCl6–solvent systems are of practical importance since these compounds are widely used catalyst precursors for hydrosilylation on an industrial scale.  相似文献   

6.
Kinetic and mechanistic studies of the homogeneous hydrogenation of cyclohexanone were carried out using the cationic complexes [MH(CO)(NCMe)2(PPh3)2]BF4 (M = Ru, Os) as the catalyst precursors, which were very efficient under mild reaction conditions in 2-methoxyethanol solution. For both complexes, the catalytic hydrogenation of cyclohexanone proceeds according to the rate law r = k[M][H2]. The activation parameters were also calculated, the activation energy for the osmium catalyst being higher than for the ruthenium(I). All experimental data are consistent with a mechanism involving the oxidative addition of hydrogen as the rate-determining step of the catalytic cycle. Finally, the [MH(CO)(NCMe)2(PPh3)2]BF4 complexes were efficient precatalysts for the selective reduction of 2-cyclohexen-1-one to cyclohexanone; the reduction of the CO group of cyclohexanone only begins to take place when the ,-unsaturated ketone has been consumed.  相似文献   

7.
The self-initiated atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in cyclohexanone (CHO) in the presence of CuCl2/N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA) is reported. The linear semilogarithmic plot of ln([M]0/[M]) vs time, the linear increase of number-average molecular weight (Mn) with conversion, and rather narrow molecular weight distributions (MWDs) have been observed, which are in agreement of the characteristics of living/controlled polymerization. The NMR spectrum revealed the existence of terminal chlorine. The chain extension further proved the living characteristic. The polymerization can only be successful using CHO as the solvent, and is well controlled at the temperature as low as 50 °C. The effects of ligand, solvent, temperature and monomer to catalyst ratio are all discussed.  相似文献   

8.
Ru(III), Rh(III), Pt(IV) and Ir(III) complexes of 2-furfural thiosemicarbazone as ligand have been synthesised. These complexes have the composition [M(ligand)2X2]X (M = Ru(III) Rh(III) and Ir(III) X = Cl and Br) and [Pt(ligand)2 X2] X2 (X = Cl, Br and 1/2SO4). The deprotonated ligand forms the complexes of the formulae M(ligand-H)3 and Pt(ligand-H)3Cl. All these complexes have been characterized by elemental analysis, magnetic measurements, electronic and infrared spectral studies. All the complexes are six-coordinate octahedral.  相似文献   

9.
Summary Square-planar and octahedral complexes of some selected bidentate N-S donor (HL) ring-substituted 4-phenylthiosemicarbazides possessing antibacterial activity have been prepared and characterized. Transformation of the red square-planar [Ni(HL)2]X2 complexes to the corresponding blue [Ni(HL)2(H2O)2]X2 octahedral complexes have been studied. The reactivity of the red square-planar complexes towards various monodentate Lewis base (B) was also examined, and octahedral complexes of the type [Ni(L)2B2] and [Ni(HL)B2]X2 were characterized. Thein vitro antibacterial activity of several of the red and blue complexes is higher than that of the unbound donors.  相似文献   

10.
《Fluid Phase Equilibria》1998,152(2):277-282
Excess molar volumes VmE have been measured using a dilatometric technique for mixtures of cyclohexanone (C6H10O) with trichloromethane (CHCl3), 1,2-dichloroethane (CH2ClCH2Cl), trichloroethene (CHClCCl2), 1,1,1-trichloroethane (CCl3CH3), and cyclohexane (c-C6H12) at T=308.15 K, and for cyclohexanone+dichloromethane (CH2Cl2) at T=303.15 K. Throughout the entire range of the mole fraction χ of C6H10O, VmE has been found to be positive for χ C6H10O+(1−χ)c-C6H12, and negative for χ C6H10O+(1−χ)CH2Cl2, χ C6H10O+(1−χ)CHClCCl2, χ C6H10O+(1−χ)CHCl3, and χ C6H10O+(1−χ) CCl3CH3. For χ C6H10O+(1−χ)CH2ClCH2Cl, VmE has been found to be positive at lower values of χ and negative at high values of χ, with inversion of sign from positive to negative values of VmE for this system occurring at χ∼0.78. Values of VmE for the various systems have been fitted by the method of least squares with smoothing equation, and have been discussed from the viewpoint of the existence specific interactions between the components.  相似文献   

11.
A series of polymeric cobalt(II), nickel(II), zinc(II) and cadmium(II) azido complexes with hydrazine of the type [M(N2H4)(H2O)(N3)Cl]n, [M(N2H4)(N3)2]n and [M(N2H4)2(N3)2]n have been prepared. These were characterized by elemental analyses, magnetic susceptibility measurements, electronic and IR spectra. The complexes are highly insoluble in polar and non polar solvents. All the complexes decompose with explosion at different temperatures between 100°C to 200°C. The magnetic moment and electronic spectral data for Co(II) and Ni(II) complexes suggest that the complexes have octahedral structure. The ligand-field parameters (10 Dq, B, β, β° and LFSE) have also been calculated for all Co(II) and Ni(II) complexes which indicate a significant covalent character of M-L bonds. The IR spectra of the complexes show that the azide group and hydrazine molecule both act as bidentate bridging ligands in [M(N2H4)(H2O)(N3)Cl]n and [M(N2H4)(N3)2]n type complexes but the azide group is terminally bonded to metal in all [M(N2H4)2(N3)2]n type complexes.  相似文献   

12.
The photochemical behaviour of the title compound 1a is compared to that of the non-fluorinated parent ketone 2-methylcyclohexanone ( 1b ). Substitution of the CH3- group on C(2) by a trifluoromethyl group strongly enhances 2H- and RH- reduction product formation in cyclohexane or 2-propanol and oxetane formation in the presence of 2-methylpropene as olefinic component. Under all these conditions 1b exclusively undergoes a-cleavage, a process observed for 1a only in non-reducing solvents as benzene or tert-butyl alcohol.  相似文献   

13.
Schiff bases derived from the condensation of β-diketones with N-methyl-S-methyldithiocarbazates yield cis dicarbonyl complexes Rh(CO)2 (Schiff) on reaction with [Rh(μ-Cl)(CO)2]2. Those derived from aromatic aldehydes form trans dicarbonyl complexes. These complexes with excess of triphenylphosphine give only Rh(CO)(PPh3)(Schiff). cis-1,5-cyclooctadiene (COD) reacts with cis dicarbonyl complexes to yield the carbonyl-free product Rh(COD)(Schiff); similar reactions have not been observed in the case of trans-dicarbonyl complexes. Oxidative addition of bromine to these complexes yields dibromo derivative in which the Schiff base acts as bidentate chelate. Rh(PPh3)2(Schiff) complexes have been obtained from the reaction of above Schiff bases with Rh(PPh3)3Cl. The structures of these new complexes have been determined based on IR and 1H NMR spectra.  相似文献   

14.
Six new dioxobridged complexes of molybdenum (IV) and tungsten (IV) with N-alkylphenothiazines having the general formula M2O4(L)2(H2O)2 [where M = molybdenum or tungsten and L = N-alkylphenothiazines] have been synthesised. The complexes have been characterised on the basis of analytical, molar conductance, magnetic susceptibility, spectral data, TGA and DTA. The low magnetic moments for the complexes are due to spin-spin interaction or metal-metal bonding. The interactions of these complexes with some biologically important amino acids have been studied.  相似文献   

15.
Summary A variety of metal(II) complexes of 2-carbethoxypyridine (L) have been prepared and characterised. With metal(II) chlorides the bis complexes can be formulated [ML2Cl2]o (M=CuII, NiII, CoII, FeII or MnII). The complexes are six-coordinate with 2-carbethoxypyridine acting as a bidentate ligandvia the pyridine nitrogen and the carbonyl group of the ester. The chloro complexes are nonelectrolytes in nitroethane; magnetic susceptibility measurements, i.r. and d-d electronic spectra are reported. With metal(II) perchlorate salts the complexes can be formulated as six-coordinate [ML2 (OH2)2] [ClO4]2 species containing ionic perchlorate. The ester exchanges of some of these complexes with a variety of primary alcohols have been investigated.  相似文献   

16.
Three mononuclear organotin(IV) complexes supported by Schiff bases have been synthesized. The complexes [(C6H5)2Sn(L)] ( 1 ), [(t‐Bu)2Sn(L)] ( 2 ) and [(t‐Bu)2Sn(L')] ( 3 ) (L, L' = deprotonated Schiff bases) were obtained in good yield by the reaction of Schiff bases H 2 L or H 2 L′ with corresponding diorganotin dichlorides respectively. All newly synthesized complexes were characterized by means of FT‐IR spectroscopy, elemental analysis and multinuclear (1H, 13C and 119Sn) NMR spectroscopy. In addition, single crystal X‐ray diffraction analyses were employed to establish the solid state molecular structures of these complexes. The structures of 1 – 3 reveal that all complexes are mononuclear with a five‐coordinated tin(IV) centre in it. The absorption and emission properties of all complexes have been investigated. Moreover, cytotoxicity and fluorescence cell imaging studies of theses complexes have been performed.  相似文献   

17.
杨晨  王国平 《无机化学学报》2018,34(12):2172-2178
以头孢氨苄(cephalexin)为原料合成锌和镍配合物,得到了2种新的单核配合物:[Ni(cepha)2]·6H2O (1)和[Zn(cepha)2]·6H2O(2)(cepha=cephalosporoate),通过元素分析、红外光谱、热重分析和X射线粉末衍射分析等方法表征1和2的结构,并通过X射线单晶衍射分析确定配合物的结构。配合物1和2均为正交晶系,空间群为P22121。头孢氨苄(cephalexin)在配位过程中发生水解产生头孢菌素中间体(cepha)并参与配位。金属离子与cepha形成六配位扭曲八面体几何构型,且通过分子间氢键将配合物进一步组装成三维网格结构。通过MTT法测定头孢氨苄、醋酸盐和配合物对乳腺癌细胞(MCF-7)和人肝癌细胞(HepG-2)的体外抗肿瘤活性,结果表明配合物1和2对MCF-7和HepG-2癌细胞均具有一定的抑制增殖活性。  相似文献   

18.
Cobalt(II) and copper(II) complexes with three dioxime ligands cyclohexylamine-p-tolylglyoxime (L1H2), tert-butyl amine-p-tolylglioxime (L2H2) and sec-butylamine-p-tolylglyoxime (L3H2), have been prepared. The metal to ligand ratios of the complexes were found to be 1?:?2. The Cu(II) complexes of these ligands are proposed to be square planar; the Co(II) complexes are proposed to be octahedral with water molecules as axial ligands. Ligands and complexes are soluble in common solvents such as DMSO, DMF, CHCl3 and C2H5OH. The ligands have been characterized by elemental analysis, IR, UV-VIS, 1H?NMR, 13C?NMR and thermogravimetric analysis (TGA). The complexes were characterized by elemental analysis, IR, UV-VIS, magnetic susceptibility measurements, thermogravimetric analysis (TGA) and electrochemistry. Electrochemical properties of metal complexes show quasi-reversible one-electron redox processes. However, Co(L1H)2 and Cu(L1H)2 complexes show another oxidation peak in the positive region. This single irreversible oxidation peak is caused by the cyclic ring of the ligand. Data also revealed that the electron transfer rates of metal complexes with L1H2 are higher than the other complexes.  相似文献   

19.
Summary Dioxomolybdenum(VI) complexes [MoO2L]H2O and oxomolybdenum(V) complexes [Mo2O3L2]H2O and [Mo2O3(LH)2(OH)2(H2O)2] (where LH2=thiocarbohydrazones derived from thiocarbohydrazide with salicylaldehyde, 5-methyl-, 5-chloro-, 5-bromo-, 3-methoxysalicylaldehyde and 2-hydroxy-1-naphthaldehyde) have been prepared and characterised by elemental analysis, conductivity, magnetic moment, i.r., u.v-vis, e.p.r. and thermal studies. The data suggests that molybdenum(VI) complexes are non electrolytes, diamagnetic, monomeric and have distorted octahedral geometry, whereas the molybdenum(V) complexes are non electrolytes, paramagnetic and have distorted octahedral structures with possible metal intereaction via oxo bridging.  相似文献   

20.
Four metal complexes, IL-OPPh2-Ru-p-cymene (3) , IL-OPPh2-Ru-benzene (4) , IL-OPPh2-Ir-Cp* (5) , IL-OPPh2-Rh-COD (6) , have been evaluated for in vitro antioxidant activity such as 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging and reducing power activity. Maximum scavenging activity (71.43%) was obtained with IL-OPPh2-Ru-p-cymene, whereas IL-OPPh2-Rh-COD showed the highest reducing power ability. The complexes were also studied for their antimicrobial activity against three Gram-positive and three Gram-negative bacteria. In addition, DNA binding of the complexes was evaluated using calf thymus DNA. Both Ru(II) complexes exhibited good DNA-binding activity while the other complexes did not have any activity. Furthermore, ab initio quantum calculations of four complexes were also carried out using density functional theory to better understand their chemical behaviors.  相似文献   

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