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1.
New bis-chelated ZnII and CdII complexes of empirical formula, [M(mpsme)2] (mpsme=the anionic form of the tridentate ONS donor ligand formed from methylpyruvate and S-methyldithiocarbazate) have been prepared and characterized by conductance, i.r., electronic and n.m.r. spectroscopic techniques. Spectral evidence supports a six-coordinate distorted octahedral structure for these complexes. X-ray crystallographic structural analysis also confirms that, in both the [Zn(mpsme)2] and [Cd(mpsme)2] complexes, the methylpyruvate Schiff base of S-methyldithiocarbazate is coordinated to the metal ions as a uninegatively charged tridentate ONS chelating agent via the carbonyl oxygen atom, the azomethine nitrogen atom and the thiolate sulfur atom. Both complexes are assigned a distorted octahedral geometry in which the ligands are arranged meridionally around the metal ions. The distortion from regular octahedral geometry is attributable to the restricted bite angles of the ligand.  相似文献   

2.
Condensation of 2,6-diacetylpyridine (dap) with S-methyldithiocarbazate (smdtc) in a 1:2 molar ratio yields a bicondensed pentadentate Schiff base (H2dapsme) which reacts with K2MCl4 (M = PdII, PtII) giving stable complexes of empirical formula, [M(dapsme)] · 0.5Me2CO. These complexes have been characterized by a variety of physico-chemical techniques. Condensation of dap with smdtc in a 1:1 molar ratio also yields the bicondensed Schiff base (H2dapsme) as the major product, but a mono-condensed one-armed Schiff base (Hmdapsme) is also obtained as a minor product. The latter reacts with K2PdCl4 in an EtOH–H2O mixture yielding a crystalline complex of empirical formula, [Pd(mdapsme)Cl], the crystal structure of which has been determined by X-ray diffraction. The complex has a distorted square-planar structure in which the ligand is coordinated to the palladium(II) ion as a uninegatively charged tridentate chelating agent via the pyridine nitrogen atom, the azomethine nitrogen atom and the thiolate sulfur atom; the oxygen atom of the acetyl group does not participate in coordination.  相似文献   

3.
Summary New complexes of general formulae [Ni(HL)2], [ML]·H2O and [Cu(HL)X] (H2L = pyrrole-2-aldehyde Schiff bases ofS-methyl- andS-benzyldithiocarbazates; X = Cl or Br; M = NiII, CuII, ZnII or CdII) were prepared and characterized by a variety of physicochemical techniques. The Schiff bases coordinate as NS bidentate chelating agents in [Ni(HL)2] and [Cu(HL)X], and as tridentate NNS chelates in [ML] (M = NiII, CuII, ZnII or CdII). Both the [Ni(HL)2] and [NiL] complexes are diamagnetic and square-planar. Based on magnetic and spectroscopic evidence, thiolate sulphur-bridged dimeric square-planar structures are assigned to the [Cu(HL)X] and [ML] (M = NiII or CuII) complexes. The complexes ML (M = ZnII or CdII) are polymeric and octahedral.  相似文献   

4.
The products obtained by reacting ruthenium (II) complexes [RuHCl(CO)(PPh3)2(B)] [B = PPh3, pyridine (py) or piperidine (pip)] with tridentate Schiff base ligands derived by condensing salicylaldehyde or o-vanillin with o-aminophenol and o-aminothiophenol, have been characterised by analytical, i.r., electronic, 1H-n.m.r. and 31P-n.m.r. spectral studies and formulated as [Ru(L)(CO)(PPh3)(B)] (L = bifunctional tridentate Schiff base anion, B = PPh3, py or pip). An octahedral structure has been tentatively proposed for the new complexes. Some have been tested for the in vitro growth inhibitory activity against bacteria Escherichia coli, Bacillus sp. and Pseudomonas sp.  相似文献   

5.
Reactions of ruthenium(II) carbonyl complexes of the type [RuHCl(CO)(PPh3)2(B)] [B?=?PPh3, pyridine (py), piperidine (pip) or morpholine (mor)] with bidentate Schiff base ligands derived from the condensation of 2-hydroxy-1-naphthaldehyde with aniline, o-, m- or p-toluidine in a 1?:?1 mol ratio in benzene resulted in the formation of complexes formulated as [RuCl(CO)(L)(PPh3)(B)] [L?=?bidentate Schiff base anion, B?=?PPh3, py, pip, mor]. The complexes were characterized by analyses, IR, electronic and 1H NMR spectroscopy, and cyclic voltammetric studies. In all cases, the Schiff bases replace one molecule of phosphine and a hydride ion from the starting complexes, indicating that Ru–N bonds in the complexes containing heterocyclic nitrogenous bases are stronger than the Ru–P bond to PPh3. Octahedral geometry is proposed for the complexes.  相似文献   

6.
The redox reaction of bis(2-benzamidophenyl) disulfide (H2L-LH2) with [Pd(PPh3)4] in a 1:1 ratio gave mononuclear and dinuclear palladium(II) complexes with 2-benzamidobenzenethiolate (H2L), [Pd(H2L-S)2(PPh3)2] (1) and [Pd2(H2L-S)2 (μ-H2L-S)2(PPh3)2] (2). A similar reaction with [Pt(PPh3)4] produced only the corresponding mononuclear platinum(II) complex, [Pt(H2L-S)2(PPh3)2] (3). Treatment of these complexes with KOH led to the formation of cyclometallated palladium(II) and platinum(II) complexes, [Pd(L-C,N,S)(PPh3)] ([4]) and [Pt(L-C,N,S) (PPh3)] ([5]). The molecular structures of 2, 3 and [4] were determined by X-ray crystallography.  相似文献   

7.
Complexes of general formula, [M(isa-sme)2] · n(solvate) [M = Ni2+, Cu2+, Zn2+, Cd2+; isa-sme = monoanionic form of the Schiff base formed by condensation of isatin with S-methyldithiocarbazate; n = 1 or 1.5; solvate = MeCN, DMSO, MeOH or H2O] have been synthesized and characterized by a variety of physicochemical techniques. An X-ray crystallographic structure determination of the [Ni(isa-sme)2] · MeCN complex reveals a six-coordinate, distorted octahedral geometry. The two uninegatively charged, tridentate, Schiff base ligands are coordinated to the nickel(II) ion meridionally via the amide O-atoms, the azomethine N-atoms and the thiolate S-atoms. By contrast, the crystal structure of [Zn(isa-sme)2] · MeOH shows a four-coordinate distorted tetrahedral geometry. The two dithiocarbazate ligands are coordinated as NS bidentate chelates with the amide O-atom not coordinated. The structure of the copper(II) complex [Cu(isa-sme)2] · DMSO is complicated and comprises two different complexes in the asymmetric unit, one four- and the other five-coordinate. The four-coordinate copper(II) has a distorted (flattened) tetrahedral geometry as seen in the Zn(II) analogue whereas the five-coordinate copper(II) has a distorted square-pyramidal geometry with one ligand coordinated to the copper(II) ion as a tridentate (NSO) ligand and the other coordinated as a bidentate NS chelate. EPR spectroscopy indicates that in solution only one form is present, that being a distorted tetrahedral complex.  相似文献   

8.
Summary FeIII, CoII, NiII and CuII complexes of a new Schiff base, 2-phenyl-1,2,3-triazole-4-carboxalidene-2-aminophenol (PTCAP), have been synthesized and characterized by elemental analyses, molar conductance and magnetic susceptibility measurements, and by u.v.-vis., i.r. and e.p.r. spectral observations. The studies indicate an octahedral structure for the complexes with the general formula [ML2] (M = CoII, NiII or CuII.; L = PTCAP) or [M′(OH)L2] (M′ = FeIII). The i.r. spectra suggest that the ligand acts as a tridentate (NNO) donor towards CoII, NiII and CuII, and, in the FeIII complex, one of the two ligand molecules acts as a bidentate (NO) donor and the other as a tridentate donor. The M?ssbauer spectrum of the FeIII complex suggests the presence of a spin equilibrium at room temperature. Cyclic voltammograms are also recorded for the CuII and FeIII complexes.  相似文献   

9.
Treatment of [Ru(PPh3)3Cl2] with one equivalent of tridentate Schiff base 2-[(2-dimethylamino-ethylimino)-methyl]-phenol (HL) in the presence of triethylamine afforded a ruthenium(III) complex [RuCl3(κ2-N,N-NH2CH2CH2NMe2)(PPh3)] as a result of decomposition of HL. Interaction of HL and one equivalent of [RuHCl(CO)(PPh3)3], [Ru(CO)2Cl2] or [Ru(tht)4Cl2] (tht = tetrahydrothiophene) under different conditions led to isolation of the corresponding ruthenium(II) complexes [RuCl(κ3-N,N,O-L)(CO)(PPh3)] (2), [RuCl(κ3-N,N,O-L)(CO)2] (3), and a ruthenium(III) complex [RuCl2(κ3-N,N,O-L)(tht)] (4), respectively. Molecular structures of 1·CH2Cl2, 2·CH2Cl2, 3 and 4 have been determined by single-crystal X-ray diffraction.  相似文献   

10.
Reaction of tridentate Schiff bases with nickel and cadmium salts in methanol afforded two new mononuclear complexes, [Ni(L1)2] (I) and [Cd(L2)2] (II), where L1 and L2 are the anions of 2-bromo-4-chloro-6-[(3-dimethylaminopropylimino)methyl]phenol (HL1) and 2-bromo-4-chloro-6-[(3-morpholin-4-ylpropylimino)methyl]phenol (HL2), respectively. The complexes were characterized by singlecrystal X-ray diffraction (CIF files CCDC nos. 1428653 (I) and 1428654 for (II)), FT-IR, and elemental analysis. Complex I crystallizes in the monoclinic space group P2 1/c, with a = 8.8216(8), b = 14.0424(8), c = 11.8687(12) Å, β = 111.238(2)°, V = 1370.4(2) Å3, Z = 2. Complex II crystallizes in the monoclinic space group P2 1/n, with a = 9.6774(4), b = 15.8970(6), c = 20.3144(7) Å, β = 90.408(2)°, V = 3125.1(2) Å3, Z = 4. The metal atoms in the complexes are coordinated by two tridentate Schiff base ligands, forming octahedral coordination. The free Schiff bases and the complexes were assayed for antibacterial activities. Both complexes are more active against the bacteria than the free Schiff bases. Complex II has the MIC value of 0.39 μg mL–1 against Bacillus subtilis.  相似文献   

11.
Two new reduced Schiff base ligands, [HL1 = 4-{2-[(pyridin-2-ylmethyl)-amino]-ethylimino}-pentan-2-one and HL2 = 4-[2-(1-pyridin-2-yl-ethylamino)-ethylimino]-pentan-2-one] have been prepared by reduction of the corresponding tetradentate unsymmetrical Schiff bases derived from 1:1: 1 condensation of 1,2-ethanediamine, acetylacetone and pyridine-2-carboxaldehyde/2-acetyl pyridine. Four complexes, [Ni(L1)]ClO4 (1), [Cu(L1)]ClO4 (2), [Ni(L2)]ClO4 (3), and [Cu(L2)]ClO4 (4) with these two reduced Schiff base ligands have been synthesized and structurally characterized by X-ray crystallography. The mono-negative ligands L1 and L2 are chelated in all four complexes through the four donor atoms to form square planar nickel(II) and copper(II) complexes. Structures of 3 and 4 reveal that enantiomeric pairs are crystallized together with opposite chirality in the nitrogen and carbon atoms. The two CuII complexes (2 and 4) exhibit both irreversible reductive (CuII/CuI; Epc, −1.00 and −1.04 V) and oxidative (CuII/CuIII; Epa, +1.22 and +1.17 V, respectively) responses in cyclic voltammetry. The electrochemically generated CuI species for both the complexes are unstable and undergo disproportionation.  相似文献   

12.
Complexes of pyrrole‐2‐carbaldehyde thiosemicarbazones, [(C4H4N4)(H)C2=N3–N2(H)–C1(=S)–N1HR; R = Ph, H2L1; Me, H2L2; H, H2L3] with nickel(II) and palladium(II) are described. The reaction of nickel(II) acetate with H2L1 in methanol in 1:1 molar ratio yielded a complex of composition, [Ni(κ2‐N3,S‐HL1)2] ( 1 ). Likewise reaction of NiCl2 with H2L2 in 1:1 molar ratio in acetonitrile in the presence of triethylamine base followed by the addition of pyridine did not yield the anticipated [Ni(κ3‐N4,N3,S‐L2)(py)] complex, moreover a bis‐square‐planar complex, [Ni(κ2‐N3,S‐HL2)2] ( 2 ) was formed. However, in the presence of bipyridine (bipy), it yielded the addition product, [Ni(κ2‐N3,S‐HL2)22‐N, N‐bipy)] ( 3 ). Reaction of PdCl22‐P, P–PPh2–CH2–PPh2) with H2L3 in toluene in the presence of triethylamine has yielded a complex of stoichiometry, [Pd(κ3‐N4,N3,S–L3)(κ1‐P–PPh2–CH2–P(O)Ph2] ( 4 ). The ligands (HL1) and (HL2) are chelating to NiII metal atom as anions binding through N3,S‐donor atoms with pendant pyrrole groups, and (L3)2– is chelating to the PdII metal atom as dianion through N4,N3,S‐donor atoms (pyrrole is N4‐bonded). Fourth site in 4 is bonded to one P‐donor atom of PPh2–CH2–P(O)Ph2, whose pendant –PPh2 group involves auto oxidation to –P(O)PPh2 during reaction. These complexes were characterized using analytical data, IR, NMR (1H, 31P) spectroscopy and X‐ray crystallography. Complexes 1 , 2 , and 4 have square‐planar arrangement, whereas complex 3 is octahedral.  相似文献   

13.
Binuclear ruthenium(III) complexes [RuX3L]2?·?nH2O (X?=?Cl, L?=?L1, L2, L3; n?=?1, L4 and L5, X?=?Br; L?=?L3), [RuX3L1.5]2?·?nH2O (X?=?Br, L?=?L1; n?=?0, L4; n?=?6 and L5; n?=?10), and [RuX3L2]2 (X?=?Br, L?=?L2) have been isolated by treatment of hydrated RuX3 (X?=?Cl/Br) in acetone with 2-(2′-aminophenylbenzimidazole) (L1), 2-(3′-aminophenylbenzimidazole) (L2), 2-[(3′-N-salicylidinephenyl)benzimidazole] (L3), 2-(3′-pyridylbenzimidazole) (L4), and 2-(4′-pyridylbenzimidazole) (L5) in acetone. The complexes were characterized by elemental analysis, conductivity and magnetic susceptibility measurements, IR, electronic, EPR, and mass spectral studies. The complexes were dimeric; based on analytical and spectral studies, an octahedral geometry was proposed for the complexes. The synthesized complexes were screened against Gram-positive and Gram-negative bacteria and fungi.  相似文献   

14.
The chiral (ONS) dianionic Schiff base ligand benzoin thiosemicarbazone (H2L) reacts with MoO2(acac)2 to give the polymeric complex [(MoO2L) n ] (1) (Type 1). The reaction of MoO2L with pyridine (py), 3-picoline (3-pic) or 4-picoline (4-pic) gives [MoVIO2LD] (D = py, 3-pic or 4-pic) (Type 1). Further, the reaction of [MoO2L] or [MoO2LD] with PPh3 or reaction of [MoO2L] with PPh3 (plus bpy or phen, D) in the presence of donor reagents D gives [MoIVOL] or [MoIVOLD] (Type 2). On the other hand, the reaction of [MoO2L] with hydrazides (zdhH3) such as benzoylhydrazine (bhH3), isonicotinoylhydrazine (inhH3), nicotinoylhydrazine (nhH3), salicyloylhydrazine (slhH3) and thiosemicarbazide (tscH3) produced non-oxo–diazenido complexes [MoL(zdh)] (Type 3). The complexes have been characterized by elemental analyses, molar conductance, magnetic moment, electronic, i.r. and e.s.r. spectroscopic measurements.  相似文献   

15.
Ruthenium and osmium complexes of the type CpMX(PPh3)L (M = Ru; X = Cl, H, S2COC10H19, S2COMe; L & PPh3 and PHPh2; M = Os, X = Cl, Br, I, H, D, xanthogenate, dithiocarbamate, BPh4, L = PPh3). The compound CpOsCl(PPh3)2 is readily soluble in MeOH and in the solution the cation [CpOs(PPh3)2]+ is present. Upon addition of NaBPh4 a white compound CpOs(PPh3)2BPh4 immediately precipitates, which can not be solved in MeOH, contrary to the behaviour of the corresponding ruthenium compound.  相似文献   

16.
Summary The reaction of warm alcoholic solutions of acetates of CoII, MnII, ZnII and NiII with 2, 6-diacetylpyridine andS-methylisothiosemicarbazide hydrogen iodide yielded the complexes: [Co(H2L)I2]·H2O, [Mn(H2L)(MeOH)2]I2, [Zn(H2L)(MeOH)I]I and [Ni(HL)]I, (H2L=the pentadentate pentaaza-ligand 2, 6-diacetylpyridine bis(S-methylisothiosemicarbazone)). The reaction of methanolic solutions of [Ni(HL)]I and NH4NCS or LiOAc.2H2O, give [Ni(HL)]NCS and NiL, respectively. For the complexes of CoII, MnII and ZnII, a pentagonal bipyramidal configuration is proposed, with H2L in the equatorial plane and two unidentate ligands (I and/or MeOH) in the axial positions. The complexes [Ni(HL)]X (X=I or NCS) and NiL probably have monomeric five- and dimeric six-coordinate structures, respectively, in which only the chelate ligand is involved in coordination.  相似文献   

17.
Summary The chelating behaviour of two biologically active ligands, pyridine-2-carboxaldehyde(4-phenyl) thiosemicarbazone(L1H) and pyridine-2-carboxaldehyde thiosemicarbazone(LH), towards FeIII, CoIII, FeII and RhIII has been investigated. The ligands act as tridentate N–N–S donors, resulting in the formation of bis-chelate complexes of the type MIII(A)2X·nH2O (A=L1 or L; X=Cl, ClO4; M=CoIII, RhIII, FeIII), FeII(L1H)2SO4·2H2O and FeII(L1)2·H2O. Biological activity of the ligands and the metal complexes in the form ofin vitro antibacterial activities towardsE. coli has been evaluated and the possible reasons for enhancement of the activity of ligands on coordination to metal ion is discussed.  相似文献   

18.
Nickel(II) complexes of general empirical formula, NiLX·nH2O (L = deprotonated form of the Schiff base formed by condensation of N-methyl-S-methyldithiocarbazate with 2-hydroxybenzaldehyde or 5-bromo-2-hydroxybenzaldehyde; X = Cl, Br, NCS, AcO or CN; n = 0, 1) have been prepared and characterized by a variety of physico-chemical techniques. Magnetic and spectroscopic data support a square-planar structure for these complexes. The crystal structure of the [Ni(ONMeS)CN]·H2O complex (ONMeS = anionic form of the 2-hydroxybenzaldehyde Schiff base of N-methyl-S-methyldithiocarbazate) has been determined by X-ray diffraction. The complex has a distorted square-planar structure in which the Schiff base is coordinated to the nickel(II) ion as a uninegatively charged anion coordinating via the phenolic oxygen atom, the azomethine nitrogen atom and the thione sulfur atom. The fourth coordination position is occupied by a cayano ligand. The antifungal properties of the Schiff bases and their nickel(II) complexes were studied against three plant pathogenic fungi. The ligands display moderate fungitoxicities against these organisms but their nickel(II) complexes are less active than the free ligands.  相似文献   

19.
Summary Schiff bases (HL) produced by the condensation ofN-methyl-S-methyldithiocarbazate with -diketones and aromatic aldehydes or ketones react with [RuHClCO(PPh3)3] to yield hexacoordinated complexes of the type [RuClCO(PPh3)2(L)]. These Schiff bases react with [RuCl2{P(OR)3}4] in 11 molar ratio to yield [RuCl{P(OR)3}2(L)] in which L is a tridentate. The chlorine atom in the complex can be removed in coordinating solvents in the presence of anions such as [BPh4] to give cationic complexes. Bis chelate complexes, [Ru{P(OR)3}2(L)2] are prepared from 12 molar proportions of the reactants. These complexes were characterised by elemental analyses, i.r.,1H n.m.r., u.v. and conductivity studies.NCL Communication No. 4224.  相似文献   

20.
Azo compounds were prepared by the reaction between benzenediazonium chloride and 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid monosodium salt under alkaline conditions. Two new azo-linked Schiff base ligands, 4-(3-methoxysalicylidene)-5-hydroxy-6-(2-hydroxyphenylazo)-2,7-naphthalene disulfonic acid disodium salt (H2L) and 4-(3-methoxysalicylidene)-5-hydroxy-6-(2-hydroxy-4-cholorophenylazo)-2,7-naphthalenedisulfonic acid disodium salt (H2L1), have been synthesized. Also, the new CuII, NiII and CoII complexes of the azo-linked Schiff base ligands were prepared and characterized by infrared spectra, UV–Vis, 1H- and 13C-n.m.r., attached proton test (APT) and distortionless enhancement by polarization transfer (DEPT) and atomic absorption spectroscopy, mass spectrocopy, elemental analyses, thermogravimetric analysis, conductivity and magnetic measurements. It was determined that the synthesized ligands were comprised of six-membered rings due to intramolecular hydrogen bonding. The results suggested that condensation of the azo-derivative compounds and o-vanillin in a 1:1 molar ratio produces mononuclear Schiff base ligands with an ONO donor set. Preliminary histological studies were made. Magnetic moment studies showed that all complexes have a tetrahedral configuration.  相似文献   

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