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1.
Reaction of RuCl2(PPh3)3 with N‐Phenyl‐pyridine‐2‐carbaldehyde thiosemicarbazone (C5H4N–C2(H)=N3‐N2H–C1(=S)N1HC6H5, Hpytsc‐NPh) in presence of Et3N base led to loss of ‐N2H‐proton and yielded the complex [Ru(pytsc‐NPh)2(Ph3P)2] ( 1 ). Similar reactions of precursor RuCl2[(p‐tolyl)3P]3 with a series of thiosemicarbazone ligands, viz. pyridine‐2‐carbaldehyde thiosemicarbazone (Hpytsc), salicylaldehyde thiosemicarbazone (H2stsc), and benzaldehyde thiosemicarbazone (Hbtsc), have yielded the complexes, [Ru(pytsc)2{(p‐tolyl)3P}2] ( 2 ), [Ru(Hstsc)2{(p‐tolyl)3P}]2 ( 3 ), and [Ru(btsc)2{(p‐tolyl)3P}2] ( 4 ), respectively. The reactions of precursor Ru2Cl4(dppb)3 {dppb = Ph2P–(CH2)4–PPh2} with H2stsc, Hbtsc, furan‐2‐carbaldehyde thiosemicarbazone (Hftsc) and thiophene‐2‐carbaldehyde thiosemicarbazone (Httsc) have formed complexes of the composition, [Ru(Hstsc)2(dppb)] ( 5 ), [Ru(btsc)2(dppb)] ( 6 ), [Ru(ftsc)2(dppb)] ( 7 ), and [Ru(ttsc)2(dppb)] ( 8 ). The complexes have been characterized by analytical data, IR, NMR (1H, 31P) spectroscopy and X‐ray crystallography ( 1 and 5 ). The proton NMR confirmed loss of –N2H– proton in all the compounds, and 31P NMR spectra reveal the presence of equivalent phosphorus atoms in the complexes. In all the compounds, thiosemicarbazone ligands coordinate to the RuII atom via hydrazinic nitrogen (N2) and sulfur atoms. The arrangement around each metal atom is distorted octahedral with cis:cis:trans P, P:N, N:S, S dispositions of donor atoms.  相似文献   

2.
A series of new hexa‐coordinated ruthenium(II) hydroxyquinoline–thiosemicarbazone complexes of the type [Ru(CO)(EPh3)(B)(L)] (E = P or As; B = PPh3, AsPh3 or Py; L = hydroxyquinoline–thiosemicarbazone) were synthesized by reacting ruthenium precursor complexes [RuHCl(CO)(EPh3)2(B)] (E = P or As; B = PPh3, AsPh3 or Py) with hydroxyquinoline–thiosemicarbazone ligands in ethanol. The new complexes were characterized by analytical and spectroscopic (FT‐IR, UV–visible, NMR (1H, 13C and 31P) and fast atom bombardment (FAB)–mass spectrometric methods. Based on the spectral results, an octahedral geometry was assigned for all the complexes. The new complexes showed good catalytic activity for the conversion of aldehydes to amides in the presence of hydroxylamine hydrochloride–sodium bicarbonate and for the oxidation of alkanes into their corresponding alcohols and ketones in the presence of m‐chloroperbenzoic acid. The complexes also catalyzed the N‐alkylation of benzylamine in the presence of KOtBu in alcohol medium. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

3.
A series of new hexa-coordinated ruthenium(II) complexes of the type [Ru(CO)(EPh3)(B)(L)] (E = P or As; B = PPh3, AsPh3 or Py; L = chalcone thiosemicarbazone) have been prepared by reacting [RuHCl(CO)(EPh3)2(B)] (E = P or As; B = PPh3, AsPh3 or Py) with chalcone thiosemicarbazones in benzene under reflux. The new complexes have been characterized by analytical and spectroscopic (IR, UV-vis, 1H, 31P and 13C NMR) methods. On the basis of data obtained, an octahedral structure was assigned for all of the complexes. The chalcone thiosemicarbazones behave as dianionic tridentate O, N, S donors and coordinate to ruthenium via the phenolic oxygen of chalcone, the imine nitrogen of thiosemicarbazone and thienol sulfur. The new complexes exhibit catalytic activity for the oxidation of primary and secondary alcohols to their corresponding aldehydes and ketones and they were also found to be efficient catalysts for the transfer hydrogenation of carbonyl compounds.  相似文献   

4.
Three complexes of the general formula M{CpFe(η5-C5H4CH=N–N=C(S)NH2}2 [where M = NiII ( 2a ), PdII ( 2b ) and ZnII ( 2c )] were synthesized with formylferrocene thiosemicarbazone ( 1 ) as a bidentate ligand. All compounds were characterized using conventional spectroscopic and analytical techniques (infrared, 1H and 13C NMR, mass spectrometry and elemental analysis). The molecular structure of 2b was confirmed by single-crystal X-ray analysis. To study the photocatalytic activity of the new complexes ( 2a–c ), methylene blue (MB) was selected as a model pollutant. After 180 min, the degradation efficiency of MB reached 87% for 2a , 76% for 2b and 85% for 2c , and all complexes showed a higher photocatalytic activity than the formylferrocene thiosemicarbazone free ligand 1 . Theoretical studies were used to characterize the geometry and electronic structure of the compounds and to provide a rational explanation for the measured photocatalytic activity.  相似文献   

5.
The reaction of [RuHCl(CO)(B)(EPh3)2] (where E = As, B = AsPh3; E = P, B = PPh3, py, pip, or mor) and dehydroacetic acid thiosemicarbazone (abbreviated as H2dhatsc where H2 stands for the two dissociable protons) in benzene under reflux afford a series of new ruthenium(II) carbonyl complexes containing dehydroacetic acid thiosemicarbazone of general formula [Ru(dhatsc)(CO)(B)(EPh3)] (where E = As, B = AsPh3; E = P, B = PPh3, py, pip or mor; dhatsc = dibasic tridentate dehydroacetic acid thiosemicarbazone). All the complexes have been characterized by elemental analyses, FT-IR, UV-Vis, and 1H NMR spectral methods. The thiosemicarbazone of dehydroacetic acid behaves as dianionic tridentate O, N, S donor and coordinates to ruthenium via phenolic oxygen of dehydroacetic acid, the imine nitrogen of thiosemicarbazone and thiol sulfur. In chloroform solution, all the complexes exhibit metal-to-ligand charge transfer transitions (MLCT). The crystal structure of one of the complexes [Ru(dhatsc)(CO)(PPh3)2] (1) has been determined by single crystal X-ray diffraction which reveals the presence of a distorted octahedral geometry in the complexes. All the complexes exhibit an irreversible oxidation (RuIII/RuII) in the range 0.76-0.89 V and an irreversible reduction (RuII/RuI) in the range −0.87 to −0.97 V. Further, the free ligand and its ruthenium complexes have been screened for their antibacterial and antifungal activities. The complexes show better activity in inhibiting the growth of bacteria Staphylococcus aureus and Escherichia coli and fungus Candida albicans and Aspergillus niger. These results made it desirable to delineate a comparison between free ligand and its ruthenium complexes.  相似文献   

6.
The reactions of 5-R-2-hydroxybenzaldehyde-4-allyl-thiosemicarbazone {R: H (L1); Br (L2)} with [MII(PPh3)nCl2] (M = Ni, n = 2 and M = Ru, n = 3) in a 1:1 molar ratio have given stable solid complexes corresponding to the general formula [Ni(L)(PPh3)] and [Ru(HL)2(PPh3)2]. While the 1:1 nickel complexes are formed from an ONS donor set of the thiosemicarbazone and the P atom of triphenylphosphine in a square planar structure, the 1:2 ruthenium complexes consist of a couple from each of N, S and P donor atoms in a distorted octahedral geometry. These mixed-ligand complexes have been characterized by elemental analysis, IR, UV–Vis, APCI-MS, 1H and 31P NMR spectroscopies. The structures of [Ni(L2)(PPh3)] (II) and [Ru(L1H)2(PPh3)2] (III) were determined by single crystal X-ray diffraction.  相似文献   

7.
A mixed-ligand silver(I) complex of triphenylphosphine and N,N′-dibutylthiourea (Dbtu), [Ag(Ph3P)2(Dbtu)2]NO3, is prepared and its structure in the solid state is determined by X-ray crystallography. X-ray structure of this complex shows that it is mononuclear with the silver atom coordinated by two PPh3 and two dibutylthiourea ligands adopting a distorted tetrahedral geometry. The crystal structure shows the formation of 1-D chains through intermolecular hydrogen bonding interactions between N-H of Dbtu and nitrate ions. The new complex is also characterized by IR and NMR (1H and 31P) spectroscopy. The spectroscopic data are discussed in terms of the nature of bonding. A similar mixedligand complex is also prepared for tetramethylthiourea (Tmtu), but the structure of the resulting compound shows that it is a bis(phosphine) complex, [Ag(PPh3)2NO3] rather than a mixed-ligand complex.  相似文献   

8.
New ruthenium(II) complexes, [Ru(CO)(B)(LL)(PPh3)] (where, LL = tridentate Schiff bases; B = PPh3, pyridine, piperidine or morpholine) have been prepared by reacting [RuHCl(CO)(PPh3)3] or [RuHCl(CO)(PPh3)2(B)] with Schiff bases containing donor groups (O, N, X) viz., salicylaldehyde thiosemicarbazone (X = S), salicylaldehyde semicarbazone (X = O), o-hydroxyacetophenone thiosemicarbazone (X = S) and o-hydroxyacetophenone semicarbazone (X = O). The new complexes were characterised by elemental analysis, spectral (i.r., 1H- and 31P-n.m.r.), data.  相似文献   

9.
A series of 2-(1H-benzimidazol-2-yl)-phenols and their nickel complexes have been synthesized and characterized by elemental and spectroscopic analysis. The molecular structures of ligand L4 and complex C5 were confirmed by X-ray diffraction analysis. X-ray crystallographic analysis revealed that complex C5 has a six-coordinated distorted octahedral geometry. Upon activation with Et2AlCl, these nickel(II) complexes showed good activity for ethylene oligomerization. When PPh3 was added as an auxiliary ligand to the catalytic system, an increased activity as high as 1.60 × 10g mol−1 (Ni) h−1 was observed. The ligand environment and reaction conditions remarkably affected the catalytic behavior of these nickel complexes.  相似文献   

10.
Twelve coordinate lanthanide (III) complexes with the general composition [Ln L3Xn(H2O)n] where Ln = Pr(III), Sm(III), Eu (III), Gd (III), Tb (III), Dy (III), X = Cl?1, NO3 ?2, n = 2–7, and L is 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1- thiosemicarbazone have been prepared. The lanthanide complexes (5) were derived from the reaction between 1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)prop-2-en-1-thiosemicarbazone (4) with an aqueous solution of lanthanide salt. Chalcone thiosemicarbazone ligand (4) was prepared by the reaction of [1-(4-chlorophenyl)-3-(4-fluoro/hydroxyphenyl)]prop-2-enone (chalcone) (3) with thiosemicarbazide in the presence of hot ethanol. All the lanthanide-ligand 1:3 complexes have been isolated in the solid state, are stable in air, and characterized on the basis of their elemental and spectral data.

Thiosemicarbazone ligands behave as bidentate ligands by coordinating through the sulfur of the isocyanide group and nitrogen of the cyanide residue. The probable structure for all the lanthanide complexes is also proposed. The chalcone thiosemicarbazone ligands and their lanthanide complexes have been screened for their antifungal and antibacterial studies. Some of the synthesized lanthanide complexes have shown enhanced activity compared with that of the free ligand.

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.  相似文献   

11.
12.
Reactions of copper(I) halides with triphenyl phosphine in acetonitrile followed by the addition of salicylaldehyde N-ethylthiosemicarbazone {(2-OH–C6H4)(H)C2=N3–N2H–C1(=S)N1HEt, H2stsc-NEt} in chloroform in 1?:?2?:?1 (Cl) or 1?:?1?:?1 (Br, I) molar ratios yield mononuclear, [CuCl(η 1-S-H2stsc-NHEt)(PPh3)2] (1) and sulfur-bridged dinuclear, [Cu2X2(μ-S-H2stsc-NEt)2(PPh3)2] (X?=?Br, 4; I, 5) complexes. Similarly, reaction of silver halides (Cl, Br) with H2stsc-NEt in acetonitrile followed by the addition of PPh3 to the solid that formed (1?:?1?:?2 molar ratio), yielding mononuclear complexes, [AgX(η 1-S-H2stsc-NHEt)(PPh3)2] (Cl, 2; Br, 3). All these complexes are characterized with analytical data, IR, and NMR spectroscopy and single-crystal X-ray crystallography. The ligand favored η 1-S bonding in 1, 2, and 3, and μ-S bonding in 4 and 5. Cu?···?Cu contacts were 3.063?Å. The complexes form 1-D or 2-D H-bonded networks, entrapping solvent in some cases.  相似文献   

13.
Several new hexa-coordinated ruthenium(II) and penta-coordinated rhodium(I) complexes of the types [RuCl(CO)(PPh 3 ) 2 (TSC)], [RuH(CO)(PPh 3 ) 2 (TSC)], and [Rh(PPh 3 ) 3 (TSC)] (where TSC = anion of thiosemicarbazone Schiff bases) have been prepared by the reactions of [RuHCl(CO)(PPh 3 ) 3 ], [RuH 2 (CO)(PPh 3 ) 3 )], and [RhH(PPh 3 ) 4 ] with thiosemicarbazones of 2-furaldehyde (H-FTSC), thiophene-2-carboxaldehyde (H-TCTSC), p-anisaldehyde (H-ATSC), piperonaldehyde (H-PTSC), and cyclohexanone (H-CTSC). All the new complexes obtained have been characterized on the basis of elemental analysis, IR, 1 H NMR, 31 P NMR, and electronic spectral data.  相似文献   

14.
Two new complexes, [MnL2](ClO4) (1) and [CuL2] (2) (where LH = (E)-1-((3-(dimethylamino)propylimino)methyl)naphthalen-2-ol), have been synthesized and characterized by spectroscopic techniques and their molecular structures are established by single-crystal X-ray diffraction study. Complex 1 adopts an octahedral geometry around the central manganese atom which is in + 3 oxidation state, whereas in complex 2, the Cu+2 ion preferred a square pyramidal environment around it through the ligand donor atoms. Both complexes were tested for catecholase and phenoxazinone synthase activity. Complex 1 catalyzes the oxidation of 3,5-ditertiary-butyl catechol with a kcat value of 6.8424 × 102 h?1 in acetonitrile whereas the same for complex 2 is 3.7485 × 102 h?1 in methanol. Phenoxazinone synthase activity was shown only by complex 2 having kcat = 74.225 h?1. Structures of both the title complexes have been optimized by means of DFT calculations. Experimental electronic spectra of the complexes have been corroborated by TDDFT analysis. Electrochemical investigations by means of cyclic voltammetry have been carried out to study the electron transfer processes in the complexes.  相似文献   

15.
Mixed ligand silver(I) complexes of triphenylphosphine and thioureas (thiourea (Tu), N-methylthiourea (Metu), N,N′-dimethylthiourea (Dmtu) and N,N′-diethylthiourea (Detu)) with the general formulae, [(Ph3P)2Ag(thione)]NO3 and [(Ph3P)Ag(thione)2]NO3, have been prepared and characterized by elemental analysis, IR and NMR (1H, 13C and 31P) spectroscopic methods. The crystal structure of one of them has been determined by X-ray crystallography. The spectral data of the complexes are consistent with sulfur coordination of the thiones to silver(I). The single crystal X-ray structure of complex 1, {[Ag(PPh3)(thiourea)(NO3)]2·[Ag(PPh3)(thiourea)]2(NO3)2}, shows that the complex consists of two independent centrosymmetric binuclear units, each having the silver atoms coordinated to one PPh3 and two bridging thiourea molecules. In one of the independent units the silver atom is additionally bound to a nitrate ion, leading to a tetrahedral geometry, while in the other unit the silver atom adopts a trigonal planar environment. Antimicrobial activities of the complexes were evaluated by their minimum inhibitory concentration and the results showed that the complexes show a wide range of activity against two gram-negative bacteria (Escherichiacoli, Pseudomonasaeruginosa) and molds (Aspergillusniger, Penicilliumcitrinum), while the activities were poor against yeasts (Candidaalbicans, Saccharomycescerevisiae). However, the title complex did not show activity against any tested microorganism.  相似文献   

16.
The synthesis, spectral characterization, and biological studies of ruthenium(II) hydrazone complexes [RuCl(CO)(PPh3)2L] (where L = hydrazone ligands) have been carried out. The hydrazones are monobasic bidentate ligands with O and N as the donors and are preferably found in the enol form in all the complexes. The molecular structure of the ligands HL1, HL2, and HL3 were determined by single-crystal X-ray diffraction. The DNA binding studies of the ligands and complexes were carried out by absorption spectroscopic and viscosity measurements. The results revealed that the ligands and complexes bind to DNA via intercalation. The DNA cleavage activity of the complexes, evaluated by gel electrophoresis assay, revealed that the complexes are good DNA cleaving agents. The antioxidant properties of the complexes were evaluated against DPPH, OH, and NO radicals, which showed that the complexes have strong radical-scavenging. Further, the in vitro cytotoxic effect of the complexes examined on HeLa and MCF-7 cancer cell lines showed that the complexes exhibited significant anticancer activity.  相似文献   

17.
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   

18.
A series of new mixed ligand complexes of Zn(II), Cd(II), and Hg(II) with citronellal thiosemicarbazone [3,7-dimethyl-6-octene-1-a1 thiosemicarbazone (LH)] and N-phthaloyl amino acids (AH) have been synthesized by the reaction of metal(II) chloride with ligands citronellal thiosemicarbazone (DOTSC) and N-phthaloyl glycine [1,3-dihydro-1,3-dioxo-2H-isoindole-2-acetic acid (A1H)] or N-phthaloyl alanine [1,3-dihydro-1,3-dioxo-α(methyl)-2H-isoindole-2-acetic acid (A2H)] in 1:1:1 molar ratio in dry refluxing ethanol. All the complexes have been characterized by elemental analyses, molar conductance measurement, molecular weight measurement, IR, and multinuclear NMR (1H and 13C{1H}) spectral studies. IR, 1H, and 13C{1H} NMR spectral studies suggest the involvement of azomethine-N, thiol-S atoms of the thiosemicarbazone moiety and both carboxylate-O of N-phthaloyl amino acid moiety in coordination with central metal(II) ion, and four coordinated geometries have been assigned to these complexes. The free ligands and metal complexes have been screened for their antifungal activity against two fungal strains, Fusarium moniliformae and Macrophomina phaseolina, using the the radial growth method. The results of antifungal activity show that metal complexes show enhanced higher activity than the free ligands.

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.  相似文献   

19.
Reactions of 5-bromo-2-hydroxy-benzaldehyde-S-R-4-R1-thiosemicarbazones, [R, R1 = H,H (L1); CH3, H (L2); H, C6H5 (L3); CH3, C6H5 (L4)] with [Ni(PPh3)2Cl2] in 1:1 molar ratio yielded complexes of general formula [Ni(L)(PPh3)]. While the complexes of L1 and L3 involve the ONS donor set of the thiosemicarbazone, the L2 complexes utilize the ONN set. The reaction of L4 and the nickel salt gave the L3 complex by loss of the CH3 group from the sulphur. The complexes were characterized by physico-chemical and spectroscopic methods. The structures of the L1 and L2 complexes have been determined by single crystal X-ray diffraction and a new coordination mode (ONN) of salicylaldehyde thiosemicarbazones has been identified. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

20.
Reactions of [RuHCl(CO)(B)(EPh3)2] (B = EPh3 or Py; E = P or As) and chalcones in benzene with equal molar ratio led to the formation of new complexes of the type [RuCl(CO)(EPh3)(B)(L1?4)] (B = PPh3, AsPh3 or Py; E = P or As; L = chalcone). The new complexes have been characterized by analytical and spectroscopic (IR-, electronic, 1H-, 31P-, and 13C-NMR) data. Based on these data, an octahedral structure has been assigned for all the complexes. The chalcones are monobasic bidentate (O,O) donors and coordinate to ruthenium via phenolic and carbonyl oxygen. The new complexes exhibit efficient catalytic activity for the transfer hydrogenation of carbonyl compounds. Antifungal properties of the ligands and their complexes have been examined and compared with standard Bavistin.  相似文献   

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