含水杨醛缩对硝基苯甲酰腙的钒酰配合物和钴配合物的合成和晶体结构

本文合成了含水杨醛缩对硝基苯甲酰腙(简写为H2L)的钒酰配合物VOL(CH3OH)(CH3O)(1,C16H16N3O7V,Mr=413.26)和钴配合物[CoL(C5H5N)3]NO3C5H5N(2,C34H29N8O7Co,Mr=720.58)。配合物1属单斜晶系,空间群为P21/c,a=7.3253(3),b=18.8237(9),c=12.9014(5)?b=91.672(1),V=1778.2(1)3,Z=4,F(000)=848,m(MoKa)=0.603mm1,R=0.0470,wR=0.1312。配合物2属单斜晶系,空间群为P21/c,a=11.4196(8),b=17.157(1),c=17.081(1)?b=96.8233(9),V=3323.0(4)3,Z=4,F(000)=1488,m(MoKa)=0.578mm1,R=0.0455,wR=0.1311。在配合物1中,钒(V)原子由周围的酰氧基原子、配体L2的3个配位原子,去质子化甲醇的甲氧基原子和配位甲醇的氧原子配位,形成畸变的VO(ONO)(O)(O)八面体配位构型。晶体内每2个分子间通过氢键作用缔合成中心对称的分子对,OH…N氢键键长为2.861(4)?键角163.20。晶体中存在着弱p-p共轭作用。在配合物2中,钴(Ⅲ)原子由1个L2的3个配位原子和3个配位吡啶分子的3个氮原子配位,呈N4O2八面体配位构型。     

Synthesis,Spectral and Electrochemical Studies of Mixed-Ligand Oxovanadium(IV) and Oxovanadium(V) Complexes Incorporating the Tridentate ONO Donor Schiff Base Derived from Acetylacetone and Benzoylhydrazine

Mixed-ligand oxovanadium(IV) and oxovanadium(V) complexes with a tridentate dinegative ONO donor Schiff base ligand [viz., 4-(1-hydroxybenzylidenehydrazono)-2-penten-2-ol (H₂L)] and bidentate NN [viz., 2,2-bipyridine (bipy) and 1,10-phenanthroline (phen): complexes (1) and (2), respectively] or OO^–[viz., ethylene glycol (H₂gol), salicylaldehyde (Hsal) and vanillin (Hvan): complexes (3)–(5), respectively] donor ligands have been prepared and characterized by elemental analyses and by i.r., e.p.r., n.m.r., and u.v.–vis. spectroscopies. The complexes with NN donor ligands are one electron paramagnetic, displaying axial e.p.r. spectra and exhibiting two ligand-field transitions in the visible region, whereas the complexes with OO^– donor ligands are diamagnetic and display only LMCT bands. ¹H n.m.r. spectral data indicate that the pentavalent complexes (4) and (5) exist in two isomeric forms [(4A), (4B) and (5A), (5B) in 1:1 and 4:1 ratios, respectively]. The vanadyl(IV) complexes display an irreversible oxidation peak near +0.67 V while among the vanadyl(V) complexes, (3), displays an irreversible reduction peak near –0.20 V and (4) and (5) display a quasi-reversible one electron reduction peak near +0.25 V versus s.c.e. The trend in redox potential values and the selective stabilization of VO²⁺ and VO³⁺ motifs have been explained on the basis of the basicity of the bidentate auxiliary ligands.     

Synthesis and Spectroscopic Characterization of Two Different Types of Heterobimetallic Glycolate Complexes of Niobium(V)

An entirely new class of heterobimetallic homoleptic glycolate complexes of the type Nb(OGO)₃{Ta(OGO)₂} [where G=CMe₂CH₂CH₂CMe₂ (G¹) (3); CMe₂CH₂ CHMe(G²) (4); CHMeCHMe (G³) (5); CH₂CMe₂CH₂ (G⁴) (6); CMe₂CMe₂(G⁵) (7); CH₂CHMeCH₂ (G⁶) (8); CH₂CEt₂CH₂ (G⁷) (9); CH₂CMe(Prⁿ)CH₂ (G⁸) (10)] have been prepared by the reactions of Nb(OGO)₂(OGOH) [G=G¹ (1a); G² (1b); G³ (1c); G⁴ (1d); G⁵ (1e); G⁶ (1f); G⁷ (1g); G⁸ (1h)] with Ta(OGO)₂ (OPrⁱ) (G=G¹ (2a); G² (2b); G³ (2c); G⁴ (2d); G⁵ (2e) G⁶ (2f); G⁷ (2g); G⁸ (2h). In addition to the novel derivatives (2)–(10), our earlier investigations on heterobimetallic glycolate-alkoxide derivatives have been extended to derivatives of the type Nb(OGO) [where M=A1 n=3, G=G³ (11);G⁴ (12); G⁶ (13) G⁷ (14); G^s (15); G⁹=CH₂CH₂CH₂ (16) and M=Ti (n=4, G=G⁴) (17), Zr(n=4,G=G⁴) (18)], which are conveniently prepared by the reactions of metalloligands Nb(OGO)₂(OGOH) [G=G³ (1c); G⁴ (1d); G⁶ (1f); G⁷ (1g); G⁸ (1h); G⁹ (1i)] with different metal alkoxides. All of these new complexes have been characterized by elemental analyses, molecular weight determinations, and spectroscopic (I.r. and ¹H, ²⁷Al-n.m.r.) studies. Structural features of the new derivatives have been elucidated on the basis of molecular weight and spectroscopic data.     

Mixed Ligand Complexes of Oxovanadium (IV) Oxalate

The oxovanadium(IV) complexes VOC₂O₄ · 2DMF, VOC₂O₄ · 2 formamide, VOC₂O₄ · 2 ethylene urea, VOC₂O₄ · 2 urea and VOC₂O₄ · en have been prepared and characterized. The oxalato group functions as a bidentate ligand in all these complexes. Except ethylene diamine the remaining ligands – DMF. formamide, ethylene urea and urea – act as monodentate ligand coordinating through their carbonyl oxygen. Ethylene diamine is bound to the metal through nitrogen. In all the complexes vanadium is five coordinated in distorted tetragonal-pyramidal structures.     

Syntheses,Structures, and Properties of Oxovanadium(V) Complexes with Ketone and Ketolate Ligands

VOCl₃ and Spiro(adamantan‐2, 2′‐homoadamantan‐3‐one) form a stable 1 : 1 complex, which has been isolated and characterised. A X‐ray structure analysis reveals a close V=O···H‐C contact supporting the presence of an analogous interaction leading to C‐H activation in the corresponding CrO₂Cl₂ complex. For both systems such geometrical arrangements are predicted by means of DFT calculations. The reaction of Spiro(adamantan‐2, 2′‐homoadamantan‐3‐one‐4‐olate), L² , with VOCl₃ leads to a complex [ L² ₂VOCl], which can be converted to the corresponding triflate [ L² ₂VO(O₃SCF₃)] via treatment with AgO₃SCF₃. The latter is a mononuclear oxovanadium(V) complex with a bulky ligand sphere where one coordination site is accessible (as the triflate ligand is quite loosely bound), and as it is furthermore soluble in organic solvents, it seems an interesting complex to start from in future experiments.     

Oxovanadium(IV) Complexes of tetradentate SCHIFF Bases

The oxovanadium(IV) complexes of the Schiff bases derived from 1,3-diamino-propane-2-ol and salicylaldehyde, 3-aldehydosalicylic acid, 5-chloro-salicylaldehyde, acetyl acetone, and also of the Schiff base derived from 1.3-diaminopropane and salicylaldehyde have been isolated in the pure state and characterized. The structure of these complexes is discussed on the basis of elemental analyses, electronic spectra and magnetic moment values. These complexes are characterized as five co-ordinate compounds having the general formula [VO](L), where, LH₂ = a molecule of dibasic, tetradentate Schiff base. Electronic spectra of the complexes are found to be solvent independent. The compounds are paramagnetic (μ_eff. = 1.76–1.79 B. M.), and are very stable in air.     

Spectroscopic and Biochemical Studies of Some Manganese(II), Oxovanadium(V) and Dioxomolybdenum(VI) Complexes S/O and N Donor Agents Synthesized under Microwave Conditions

The synthesis of some new manganese(II), oxovanadium(V) and dioxomolybdenum(VI) complexes with 5-chloro-1,3-dihydro-3-[2-(phenyl)-ethylidene]-2H-indol-2-one-hydrazinecarbothioamide (L¹H) and 5-chloro-1,3-dihydro-3-[2-(phenyl)-ethylidene]-2H-indol-2-one-hydrazinecarboxamide (L²H) were carried out in unimolar and bimolar ratios. All the new derivatives have been characterized by elemental analyses, molecular weight determinations, molar conductance, magnetic measurements, i.r., ¹H-n.m.r. and e.s.r. studies. The i.r. and n.m.r. spectral data suggest the involvement of sulphur/oxygen and azomethine nitrogen in coordination to the central metal ion. The magnetic moment values of the manganese(II) complexes are in the 5.85–6.13 B.M. range, suggesting a high spin state in these complexes. Based on these spectral studies tetrahedral geometry for the manganese(II) complexes and octahedral geometry for the molybdenum complexes has been proposed. In the case of the oxovanadium complexes vanadium is in the penta and hexa coordinated environments. Compounds have been synthesized in an open vessel under microwave irradiation (MWI) using a domestic microwave oven. The reaction time decreases from hours to minutes with improved yield as compared to conventional heating. The free ligands and their metal complexes have been tested in vitro against a number of microorganisms in order to assess their antimicrobial properties. The results indicate that the ligands and their respective metal derivatives possess antimicrobial properties.     

Acetohydroxamate-coordinated Oxovanadium(V) Complexes with Halide Containing Hydrazones: Synthesis,Characterization, X-ray Crystal Structures,and Antibacterial Activity

Russian Journal of Coordination Chemistry - Two oxovanadium(V) complexes, [VO(L)(L1)] (I) and [VOLL2] (II), where L = acetohydroxamate, H2L1 = 2-bromo-N'-(2-hydroxybenzylidene)benzohydrazide,...     

Synthesis and Spectroscopic Characterization of Silver(I) Complexes of Selenones

Silver(I) complexes of selenones, [LAgNO₃] and [AgL₂]NO₃ (where L is imidazolidine-2-selenone or diazinane-2-selenone and their derivatives) have been prepared and characterized by elemental analysis, IR and NMR (¹H, ¹³C and ¹⁰⁷Ag) spectroscopy. An upfield shift in the C=Se resonance of selenones in ¹³C NMR and a downfield shift in N-H resonance in ¹H NMR are consistent with selenium coordination to silver(I). In ¹⁰⁷Ag NMR, the AgNO₃signal is deshielded by 450-650 ppm on coordination to selenones. Greater upfield shifts in ¹³C NMR were observed for [LAgNO₃] compared to [AgL₂]NO₃complexes, whereas the opposite trend was observed for ¹H and¹⁰⁷Ag NMR chemical shifts.     

Synthesis and Characterisation of Novel Bis(diphenylphosphane oxide)methanidoytterbium(III) Complexes

Reaction of [YbCp₂(dme)] (Cp = cyclopentadienyl, dme = 1,2 dimethoxyethane) with bis(diphenylphosphano)methane dioxide (H₂dppmO₂) leads to deprotonation of the ligand H₂dppmO₂ and oxidation of ytterbium, forming an extremely air-sensitive product, [Yb^III(HdppmO₂)₃] (1), a six-coordinate complex with three chelating (OPCHPO) HdppmO₂ ligands. Complex 1 was also obtained by a redox transmetallation/protolysis synthesis from metallic ytterbium, Hg(C₆F₅)_2, and H₂dppmO₂. In a further preparation, the reaction of [Yb(C₆F₅)₂] with H₂dppmO₂, not only yielded compound 1, but also gave a remarkable tetranuclear cage, [Yb₄(µ-HdppmO₂)₆(µ-F)₆] (2) containing two [Yb(µ-F)]₂ rhombic units linked by two fluoride ligands and the tetranuclear unit is encapsulated by six bridging HdppmO₂ donors. The fluoride ligands of the cage result from C-F activation of pentafluorobenzene and concomitant formation of p-H₂C₆F₄ and m-H₂C₆F₄, the last being an unexpected product.     

Oxovanadium(V) complexes incorporating tridentate aroylhydrazoneoximes: Synthesis, characterizations and antibacterial activity

Some new oxovanadium(V) complexes, [VOL^1-3(OEt)(EtOH)] (1-3), have been reported, which were obtained from the reaction of the Schiff bases H₂L^1-3 (where H₂L¹ = the salicylhydrazone of diacetyl monoxime; H₂L² = the 4-methoxy salicylhydrazone of diacetyl monoxime and H₂L³ = the 4-hydroxy salicylhydrazone of diacetyl monoxime) with VO(acac)₂ in a 1:1 molar ratio. Three 4-R-aroylhydrazoneoximes (V) have been used as ligands in the present study, differing in the inductive effect of the substituent R (R = H, OCH₃ and OH), in order to observe their influence, if any, on the redox potentials and biological activity of the complexes. All the synthesized ligands and metal complexes were successfully characterized by elemental analysis, IR, UV-Vis and NMR spectroscopy. An X-ray diffraction study of [VOL¹(OEt)(EtOH)] (1) reveals that the metal center has a distorted octahedral O₅N coordination sphere, where the O,N,O donor ligand and the ethoxo group constitute a satisfactory O₃N basal plane. Cyclic voltammetry of the complexes show a quasi-reversible cyclic voltammetric response in the potential range 0.29-0.36 V involving a single electron V(V)-V(IV) reduction. The complexes have also been screened for their antibacterial activity against Escherichia coli, Bacillus, Proteus and Klebsiella. Minimum inhibitory concentrations of these complexes and the antibacterial activities indicate compound 1 as the potential lead molecule for drug design.     

Synthesis and Characterization of Six-Coordinate Nitrido Complexes of Vanadium(V), Chromium(V), and Manganese(V). Isolation of a Dinuclear, Mixed-Valent &mgr;-Nitrido Chromium(III)/Chromium(V) Species

Photolysis of a series of octahedral monoazido complexes of the type [LM(III)(didentate ligand)(N(3))](n)(+)X(n) of vanadium(III), chromium(III), and manganese(III) in the solid state or in solution yields quantitatively the corresponding six-coordinate nitrido complexes [LM(V)(didentate ligand)(N)](n)(+)X(n) and 1 equiv of dinitrogen. L represents the macrocycle 1,4,7-triazacyclononane or its N-methylated derivative (L'), the didentate ligands are pentane-2,4-dionate (acac), 2,2,6,6-tetramethylheptane-3,5-dionate (tacac), picolinate (pic), phenanthroline (phen), and oxalate (ox), and X(-) represents perchlorate or hexafluorophosphate. The following nitrido complexes were prepared: [LV(V)(N)(acac)](ClO(4)) (6), [LCr(V)(N)(acac)](ClO(4)) (13), [LCr(V)(N)(tacac)](ClO(4)) (14), [LCr(V)(N)(pic)](ClO(4)) (15), [LCr(V)(N)(phen)](ClO(4))(2) (16), [LCr(V)(N)(ox)] (19), [L'Mn(V)(N)(acac)]PF(6) (21). Photolysis of [LCr(III)(N(3))(ox)] (17) in the solid state produces the &mgr;-nitrido-bridged mixed-valent species [L(2)Cr(2)(ox)(2)(&mgr;-N)](N(3)) (18). The structures of the precursor complex [L'Mn(acac)(N(3))]BPh(4) (20), of 13, and of [L'Mn(V)(N)(acac)]BPh(4) (21) have been determined by X-ray crystallography. Complex 13 crystallizes in the orthorhombic space group Pnma, with cell constants a = 27.187(5) ?, b = 9.228(2) ?, c = 7.070(1) ?, V = 1773.7(6) ?(3), and Z = 4; complex 20 crystallizes in the triclinic space group P&onemacr; with a = 14.769(5) ?, b = 16.83(1) ?, c = 16.96(1) ?, alpha = 108.19(5) degrees, beta = 105.06(4) degrees, gamma = 99.78(4) degrees, V = 3719(2) ?(3), and Z = 4; and complex 21 crystallizes in the monoclinic space group P2(1)/n with a = 10.443(3) ?, b = 16.035(4) ?, c = 21.463(5) ?, beta = 95.76(1) degrees, V = 3575.9(14) ?(3), and Z = 4. The Cr(V)&tbd1;N and Mn(V)&tbd1;N distances are short at 1.575(9) and 1.518(4) ?, respectively, and indicate a metal-to-nitrogen triple bond.     

Synthesis,Characterization, and Antibacterial Studies of Oxovanadium(IV) Complexes with Thiazole-Derived Schiff Bases

Oxovanadium(IV) complexes of Schiff bases, derived from 2-amino-4-phenyl thiazole/substituted 2-amino-4-phenyl thiazoles and thiophene-2-aldehyde have been synthesized and characterized on the basis of elemental analysis, molar conductance measurements, magnetic susceptibility data, and UV-visible, and IR spectral studies. All the complexes are monomeric possessing a 1:2 (metal:ligand) stoichiometry. On the basis of these data, a square pyramidal geometry has been assigned for the complexes. A few complexes have been subjected to thermal decomposition studies. The ligands and their metal complexes have been screened for their antibacterial activities.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Syntheses,Crystal Structures,and Antimicrobial Activities of Oxovanadium(V) Complexes with Tridentate Schiff base Ligand

Russian Journal of Coordination Chemistry - Two structurally similar new oxovanadium complexes, [VO(L)(L1)] (I) and [VO(L)(L2)] (II), where L is the dianionic form of...     

Synthesis and Crystal Structure of a New Oxovanadium（V） Multicomponent Complex with Acylhydrazone and Benzoylhydrazine

A new oxovanadium（V） complex with the mixed ligand of 2-oxopropionic acid benzoylhydrazone （C10H10N2O3） and benzoylhydrazine （C7H8N2O）, VO（C7H7N2O）（C10H9N2O3）, has been synthesized. Its structure was determined by single crystal X-ray diffraction analysis. The crystal belongs to monoclinic system with space group P21/n and cell parameters： a=1.1136（4） nm, b=0.6217（2） nm, c=2.6038（9） nm, β=97.182（6）°, V= 1.7887（11） nm^3, Z=4, F（000）=836, Mr=407.28, Dc= 1.512 g/cm^3,μ （Mo Kα） =0.592 mm^-1, R1 =0.0445, wR2= 0.1203. Vanadium atom is 6-coordinated by carboxyl and carbonyl O atoms and N atom of one tridentate C10H10N2O3 to form two stable five-membered rings with the same edge, and the other coordinated atoms of N and O come from one bidentate benzoylhydrazine C7H8N2O. The title complex has a six-coordinated V center [VO（N2O3）] with a distorted octahedral arrangement. In the crystal lattice, there are hydrogen bonding interactions between two molecules.     

Synthesis and Spectroscopic Studies of Chosen Heteropolytungstates and Their Ln(III) Complexes

The heteropolytungstates [(Na)P₅W₃₀O₁₁₀]^4– (I), [(Na)Sb₉W₂₁O₈₆]^18– (II) and [(Na)As₄W₄₀O₁₄₀]^27– (III) and the monovacant Keggin structure of the general formula [XW_11–xMo_xO₃₉]^n– (X-Si, P; n = 7 for P and 8 for Si) (IV) as well as their europium(III) complexes were studied. The structures of I–IV as well as the europium(III) encrypted [(Eu)P₅W₃₀O₁₁₀]^12– (VI), [(Eu)Sb₉W₂₁O₈₆]^16– (VII), [(Eu)As₄W₄₀O₁₄₀]^25– (VIII) and sandwiched [Eu(XW_11–xMo_xO₃₉)₂]^n– (n =11 for P and n = 13 for Si) (V) complexes were synthesized and spectroscopically characterized. The complexes were studied using UV-Vis absorption and luminescence, as well as the laser-induced europium ion luminescence spectroscopy. Absorption spectra of Nd(III) were used to characterize the complexes formed. Excitation and emission spectra of Eu(III) were obtained for solid complexes and their solutions. The relative luminescence intensities of the Eu(III) ion, expressed as the ratio of the two strongest lines at 594 nm and 615 nm, = I₆₁₅/I₅₉₄, which is sensitive to the environment of the primary coordination sphere about the Eu(III) ion, was calculated. In the case of the sandwiched [Eu(XW_11–xMo_xO₃₉)₂]^n– complexes a linear dependence of the luminescence quantum yield of Eu(III) ion, , (calculated using [Ru(bpy)₃]Cl₂ as a standard) on the content of Mo (number of atoms, x) in the [Eu(XW_11–xMo_xO₃₉)₂]^n– structure was observed.     

Synthesis and Spectroscopic Characterisation of a New Class of Heterobimetallic Zirconocene(IV) Compounds

Reactions of Cp₂ZrCl₂ with homometallic complexes of aluminium containing one residual hydroxy group Al(OGO)(OGOH) and Al(L)(OGOH) [where G=G¹=CMe₂CMe₂ (1a); G=G²=CMe₂CH₂CHMe (1b); G= G³=CMe₂CH₂CH₂CMe₂ (1c) and L=L¹=OC₆H₄CH=NCH₂CH₂O, G=G¹ (2a); L=L¹, G=G² (2b); L=L¹, G=G³ (2c); L=L²=OC₁₀H₆CH=NCH₂CH₂O, G=G¹ (2d); L=L², G=G² (2e); L=L², G=G³ (2f)] in THF using Et₃N as HCl acceptor affords novel heterobimetallic compounds of the types Al(OGO)₂Zr(Cl)Cp₂ and Al(L)(OGO)Zr(Cl)Cp₂, respectively. All of these derivatives have been characterised by elemental analyses, molecular weight measurements, and spectroscopic [IR, NMR (¹H and ²⁷Al)] studies.     

Some Oxovanadium(IV) Complexes with C2v Symmetry

Synthesis of few oxovanadium (IV) complexes of C_2v symmetry with low symmetry β-diketones is described. Magnetic, infrared and electronic spectral studies of the complexes are reported. Splitting of the xy → xz, yz transition is observed at 77°K and is believed to be of vibrational origin.