The synthesis and characterization of a new (<Emphasis Type="Italic">E,E</Emphasis>)-dioxime containing 13-membered dithiadiazamacrocyclic moieties and its mononuclear complexes

A new (E,E)-dioxime, (6Z,7Z)-15,16-dihydro-14H-dibenzo[b,h][1,10,4, 7]dithiadiazacyclotride-cine-6,7(5H,8H)-dionedioxime (H ₂ L) has been synthesized by reacting cyanogen-di-N-oxide (2) with 2,2′-[propane-1,3-diylbis(thio)]dianiline (1). Mononuclear complexes (4) and (5) of this ligand have been synthesized by reacting the vic-dioxime (H₂L) with NiCl₂ · 6H₂O and CoCl₂ · 6H₂O, respectively. The BF ₂ ⁺ capped Ni(II) and Co(III) complexes (6) and (7) of the dioxime have been synthesized from (4) and (5). The new compounds were characterized by a combination of elemental analysis, ¹H- and ¹³C-n.m.r, i.r. and m.s. spectral data.     

The synthesis and characterization of a new (E,E)-dioxime and its mono and heterotrinuclear complexes containing dioxadithiadiazamacrobicyclic moieties

A new (E,E)-dioxime (2Z,3Z)-1,4,7,8,15,16-hexahydro-9,14-(ethanothioethanothioethano)quinoxalino[6,7-e] [4,7,1,10]benzodioxadiazacyclododecine-2,3,19,26-tetrone2,3-dioxime (H₂L) has been synthesized by reacting cyanogen-di-N-oxide with 2,3-diamino-6,7,14,15-tetrahydro-8,13-(ethanothioethanothioethano)dibenzo[b,h] [1,4,7,10]dioxadiazacyclodecine-17,24-dione (6). Mononuclear complexes (8, 9) of this ligand have been synthesized by reacting the vic-dioxime (H₂L) with NiCl₂ · 6H_2O and COCl₂ · 6H₂O respectively. The BF ₂ ⁺ capped cobalt(III) complex (10) of the new (E,E) vic-dioxime has been synthesized by using as precursor a hydrogen-bridged mononuclear cobalt(III) complex (9). The heterotrinuclear complex (11) has been prepared by reacting one mononuclear cobalt(III) complex (10) with [Cu(MeCN)₄]PF₆. The new compounds were characterized by a combination of elemental analysis, ¹H- and ¹³C-n.m.r, i.r. and m.s. spectral data.     

The synthesis and characterization of a new (E,E)-dioxime containing 20-membered tetraazadioxa macrocyclic moieties and its mononuclear complexes

A new (E,E)-dioxime, (2Z,3Z)-9,20-bis[(4-methylphenyl)sulfonyl]-1,4,7,8,9,10,11,12,14,15,17, 18,19,20,21,22-hexadecahydro-13,16-ethano[1,4,7,11,14,18]dioxatetraazacycloicosino[2,3-g] quinoxaline-2,3-dione dioxime (6) (H₂L) has been synthesized by reacting cyanogen-di-N-oxide (5) with 4,15-bis[(4-methylphenyl)sulfonyl]-2,3,4,5,6,7,9,10,12,13,14,15,16,17-tetradecahydro-8,11-ethano-1,18,4,8,11,15-benzodioxatetraazacycloicosine-20,21-diamine (4). Mononuclear complexes (7) and (8) of this ligand have been synthesized by reacting the vic-dioxime (H₂L) with NiCl₂.6H₂O and CoCl₂.6H₂O respectively. The BF₂⁺ capped Ni(II) and Co(III) complexes (9) and (10) of the dioxime have been synthesized from (7) and (8), respectively. The new compounds were characterized by a combination of elemental analysis, ¹H- and ¹³C-NMR, IR. and MS. spectral data.     

A new (E,E)-dioxime and its mono and heterotrinuclear complexes containing an 18-membered dithiatetraazamacrocycle

The novel (E,E)-dioxime, 5,6:ll,12:17,18-tribenzo-2,3-bis(hydroxyimino)-7,16-dithia-9, 14-dioxo-l,4,10,13-tetraazacyclooctadecane (H₂L) has been synthesized by reacting (E,E)-dichloroglyoxime (2) with 2,3:8,9:14,15-tribenzo-4,13-di-thia-6,11-dioxa-l,7,10,16-tetraazahexzadecane (3), prepared by the reaction of N,N-bis(chloroacetyl)-1, 2-phenylene-diamine (1) with 2-aminothiophenol. Mononuclear complexes (4, 5) of this ligand have been synthesized by reacting the vic-dioxime (H₂L) with K₂PtCl₄ and NiCl₂ · 6H₂O, respectively. Heterotrinuclear complexes (6)and(7) have been prepared by the reaction of (4) and (5) mononuclear complexes with [Cu(MeCN)₄]PF₆. The structures of the vic-dioxime and its mono and trinuclear complexes were identified by elemental analysis, ¹H- and ¹³C-n.m.r, i.r. and m.s. data.     

Synthesis and Biological Activity of Novel (E,E)-vic-dioximes

A novel vic-dioxime ligand containing the thiourea group, (4E,5E)-1,3-bis{4-[(4-methylphenylamino)methyl] phenyl}- 2-thiooxaimidazoline-4,5-dione dioxime, (4) mmdH₂ has been prepared from N,N′-bis{4-[(4-methylphenylamino)methyl]phenyl}thiourea, (3) mft and cyanogen di-N-oxide. Mononuclear [M(mmdH)₂], where M = Ni^II, Co^II and Cu^II complexes of the (4) mmdH₂ bidentate ligand have been obtained with a 1:2 metal:ligand ratio, as do most the vic-dioximes. The complexes are formed by coordination of N, N atoms of the ligand. The vic-dioxime ligand and its some transition metal complexes have been characterized by elemental analyses, molar conductance data, magnetic susceptibility, i.r., ¹H-n.m.r and u.v.–vis. spectroscopy. Conductivity measurements have shown that mononuclear complexes are non-electrolytes. In addition, the ligands and metal complexes were screened for antibacterial and antifungal activities by agar well diffusion techniques using DMF as solvent.     

Synthesis and structural studies of (2E,3E)-3-[(6-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}pyridin-2-yl)imino]butan-2-one oxime, ligand and its mono-, di- and trinuclear copper(II) complexes

A new dioxime ligand, (2E,3E)-3-[(6-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}-pyridin-2-yl)imino]butan-2-one oxime, (H₂Pymdo) (3) has been synthesized in H₂O by reacting 2,3-butenedione monoxime (2) with 2,6-diaminopyridine. Mono-, di- and tri-nuclear copper(II) complexes of the dioxime ligand (H₂Pymdo) and/or 1,10-phenanthroline have been prepared. The dioxime ligand (H₂Pymdo) and its copper(II) complexes were characterized by ¹H-n.m.r., ¹³C-n.m.r. and elemental analyses, magnetic moments, i.r. and mass spectral studies. The mononuclear copper(II) complex of H₂Pymdo was found to have a 1:1 metal:ligand ratio. Elemental analyses, stoichiometric and spectroscopic data of the metal complexes indicated that the metal ions are coordinated to the oxime and imine nitrogen atoms (C=N). In the dinuclear complexes, in which the first Cu(II) ion was complexed with nitrogen atoms of the oxime and imine groups, the second Cu(II) ion is ligated with dianionic oxygen atoms of the oxime groups and are linked to the 1,10-phenanthroline nitrogen atoms. The trinuclear copper(II) complex (6) was formed by coordination of the third Cu(II) ion with dianionic oxygen atoms of each of two molecules of the mononuclear copper(II) complexes. The data support the proposed structure of H₂Pymdo and its Cu(II) complexes.     

Synthesis and Structural Studies of 2-(hydroxyimino)-1-methylpropylideneamino-phenyliminobutan-2-one Oxime, Ligand and its Complexes with Cu(II) and Ni(II)

A new ligand incorporating a dioxime moiety, (2E,3E)-3-[(2-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}phenyl)imino]butan-2-one oxime, (H₂Phmdo) (3) has been prepared by reacting 2,3-butanedionemono-{O-[4-(1-methyl-2-oxo-propylideneaminooxy)-2,3-bis-(1-methyl-2-oxo-propylideneaminooxy-methyl)-but-2-enyl]-oxime} (2) with 1,2-phenylenediamine. Mono-, di- and trinuclear copper(II) and/or nickel(II) complexes of H₂Phmdo were characterized by elemental analyses, magnetic moments, ¹H-n.m.r. and ¹³C-n.m.r., i.r. and mass spectral studies. The mononuclear copper(II) and nickel(II) complexes of H₂Phmdo were found to have a 1:1 metal:ligand ratio. Elemental analyses, stoichiometric and spectroscopic data of the metal complexes indicated that the metal ions are coordinated to the oxime and imine nitrogen atoms (C=N). In the dinuclear complexes, in which the first Cu^(II) or Ni^(II) ion was complexed with nitrogen atoms of the oxime and imine groups, the second Cu^(II) ion is ligated with dianionic oxygen atoms of the oxime groups and are linked to the 1,10-phenanthroline nitrogen atoms. The data support the proposed structure of H₂Phmdo and its complexes.     

Studies on mononuclear transition metal chelates derived from a novel ( E,E )-dioxime: synthesis,characterization and biological activity

A novel vic-dioxime ligand with a thiourea moiety, (4E,5E)-1,3-bis{4-[(4-bromophenylamino)methylene]phenyl}-2-thiooxaimidazoline-4,5-dione dioxime (4) (bmdH₂) has been synthesized from N,N′-bis{4-[(4-bromophenylamino)methylene]phenyl}thiourea and (E,E)-dichloroglyoxime. The bmdH₂ ligand (4) forms transition metal complexes [M(bmdH)₂] with a metal?:?ligand ratio of 1?:?2 with M?=?Ni(II), Co(II), and Cu(II). The mononuclear Ni(II), Co(II) and Cu(II) complexes, [Ni(bmdH)₂] (5), [Co(bmdH)₂] (6) and [Cu(bmdH)₂] (7) have the metal ions coordinated through the two N,N atoms, as do most vic-dioximes. Elemental analyses, molar conductivity, magnetic susceptibility, IR, ¹H NMR spectra, and UV-Visible spectroscopy were used to elucidate the structures of the ligand and its complexes. Conductivity measurements have shown that the mononuclear complexes are non-electrolytes. In addition, the ligands and metal complexes were screened for antibacterial and antifungal activities by agar well diffusion techniques using DMF as solvent.     

Mono-, di- and trinuclear copper(II) dioxime complexes; 3-{2-[2-(2-hydroxyimino-1-methylpropylideneamino)ethylamino]ethylimino}butan-2-one oxime

A new ligand incorporating a dioxime moiety, 3-{2-[2-(2-hydroxyimino-1-methylpropylideneamino)ethylamino]ethylimino}butan-2-one oxime, (H₂mdo), has been synthesized and its mono-, di- and trinuclear copper(II), and hetero-dinuclear copper(II)–manganese(II) complexes have been prepared and characterized by elemental analyses, magnetic moments, ¹H- and ¹³C-n.m.r., i.r. and mass spectral studies. A mononuclear copper(II) complex of H₂mdo was found to have a 1:1 metal:ligand ratio. Elemental analyses, stoichiometric and spectroscopic data of the metal complexes indicated that the metal ions are coordinated to the oxime and imine nitrogen atoms (C=N); the data support the proposed structure of H₂mdo and its complexes.     

Effect of Structure and Composition of Copper and Cobalt Complexes with Schiff Base Ligands on their DNA/Protein Interaction and Cytotoxicity

Four transition metal complexes, namely Cu₂Cl₂(HL¹)₂ ( 1 ), Co(HL¹)₂ ( 2 ), Cu(HL²)₂ ( 3 ), Co(HL²)₃ ( 4 ) {H₂L¹ = 2‐{[2‐(2‐hydroxy‐ethoxy)‐ethylimino]‐methyl}‐phenol, H₂L² = 3‐{[2‐(2‐hydroxy‐ethoxy)‐ethylimino]‐methyl}‐naphthalen‐2‐ol} were synthesized and characterized by single‐crystal X‐ray diffraction, IR spectroscopy, and elemental analysis. The interactions of these copper and cobalt complexes with calf thymus DNA (CT‐DNA) were studied by absorption and emission titration spectroscopic methods. The interactions of these copper and cobalt complexes with bovine serum albumin (BSA) were also investigated using fluorescence, UV/Vis, and synchronous fluorescence spectroscopy. Further, the in vitro cytotoxic effect of the complexes are examined on human colon carcinoma cell lines (HCT‐116) and human lung carcinoma cell line (A549).     

Synthesis and characterization of a new vic -dioxime 6,7- bis (hydroxyimino)-9,10-diethylidine-5,8,9,10,11,18-hexahydro-5,8,11,18-tetraazadibenzo[a,e]cyclotetradecane-6,7,12,17-tetraone and its nickel and cobalt complexes

A new vic-dioxime 6,7-bis(hydroxyimino)-9,10-diethylidine-5,8,9,10,11,18-hexahydro-5,8,11,18-tetraazadibenzo[a,e]cyclotetradecane-6,7,12,17-tetraone (H₂L) and its hydrogen-bridged tetra- and six-coordinate complexes with Ni(II), Co(II), and Co(III) have been synthesized. The six-coordinate complexes of H₂L have pyridine and chloride as axial ligands. Hydrogen-bridge complexes were converted to their BF₂-bridged analogues by reaction with boron trifluoride etherate. Structures of the H₂L and its complexes were proposed from elemental analysis, ¹H and ¹³C NMR, IR and mass spectra.     

A new binucleating ligand incorporating four oxime groups and its copper(II), manganese(II) and cobalt(III) complexes

A new binucleating ligand incorporating four oxime groups, butane-2,3-dione O-[4-aminooxy-2,3-bis-(2-hydroxyimino-1-methyl-propylideneaminooxymethyl)-but-2-enyl]-dioxime, (H₄mto), has been synthesized and its dinuclear cobalt(III), copper(II), and homo- and hetero-tetranuclear copper(II)–manganese(II) complexes have been prepared and characterized by ¹H- and ¹³C-n.m.r., i.r., magnetic moments and mass spectral studies. Elemental analyses, stoichiometric and spectroscopic data indicate that the metal ions in the complexes are coordinated to the oxime nitrogen atoms (C=N) and the data support the proposed structure for H₄mto and its complexes. Moreover, dinuclear cobalt(III) and copper(II) complexes of H₄mto have a 2:1 metal:ligand ratio.     

The Synthesis and Characterization of a Novel ( E,E )-Dioxime and its Mono- and Heterotrinuclear Complexes Containing an 18-Membered Dioxadithiadiazamacrocycle

The novel ( E , E )-dioxime, 5,6:17,18-dibenzo-11,12-(4'-nitrobenzo)-2,3-bis(hydroxyimino)-7,16-dithia-10,13-dioxa-1,4-diazacyclooctadecane) ( H 2 L ), has been synthesized from reaction of ( E , E )-dichloroglyoxime ( 1 ) with 2,3:14,15-dibenzo 8,9-(4'-nitrobenzo)-4,13-dithia-7,10-dioxa-1,16-diazahegzadecane ( 2 ). The mononuclear Co(III) complex ( 4 ) of this dioxime was prepared by oxidation of the cobalt (II) complex. The -capped Co(III) complex ( 5 ) was synthesized by using a precursor Co(III) complex and boron trifluoride dietherate. The heterotrinuclear complexes ( 6 ) and ( 7 ) were prepared by reaction of ( 5 ) with NiCl 2 ·6H 2 O and CdCl 2 ·H 2 O, respectively. In addition, the homotrinuclear Cu(II) complex ( 8 ), has also been prepared by the reaction of this dioxime with CuCl 2 ·H 2 O. The structures of the dioxime and its complexes were identified by using elemental analysis, 1 H- and 13 C-NMR, IR, and mass spectral data.     

Homo- and heteronuclear complexes of a new,vicinal dioxime ligand

A new symmetrical vicinal dioxime, N,N′-bis-{4-[[(2-hydroxyphenyl)methylene]hydrazinecarbonyl]phenyl}diaminoglyoxime (LH₄), was prepared by reacting anti-dichloroglyoxime with salicylaldehyde 4-aminobenzoylhydrazone. The reaction of ligand with Ni²⁺ salts gave mono-and homopentanuclear complexes, [Ni(LH₃)₂] and [Ni₅(LH)₂X₂]. Furthermore, heteropentanuclear complexes of dioxime ligand, [Cu₄Ni(LH)₂X₄], were prepared by the reaction of [Ni(LH₃)₂)] with Cu²⁺ salt and a monodentate ligand (X = SCN⁻, CN⁻, or N ₃ ⁻ ). The structures of both the new symmetrical vicinal dioxime and its complexes were identified by elemental analyses, IR, ¹H NMR, UV-VIS spectra, and magnetic susceptibility. The elemental analyses and spectral data indicate that the hydrazone side of ligand acts as a O,N,O′ tridentate and the fourth position is occupied with monodentate anion such as SCN⁻, CN⁻, N ₃ ⁻ .     

Synthesis and characterization of novel (<Emphasis Type="Italic">E</Emphasis>,<Emphasis Type="Italic">E</Emphasis>)-dioxime and its mono- and polynuclear metal complexes containing azacrown moieties

The novel (E,E)-dioxime,7,8-bis(hydroxyimino)-1,14-bis(monoaza[8]crown-6)-benzo[f]-4,11-dioxa-1,14-diazadecane[7,8-g]quinoxaline (H₂L), has been synthesized by the reaction of 6,7-diamino-1,12-bis(monoaza[18]crown-6)benzo[f]-4,9-dioxa-1,12-diazadecane (4) which has been prepared by the reduction of 6,7-dinitro-1,12-bis(mono-aza[18]crown-6)benzo[f]-4,9-dioxa-1,12-diazdecane (3) and cyanogendi-N-oxide. Mononuclear Ni^II and Cu^II complexes of H₂L have a metal:ligand ratio of 1:2 and the ligand coordinates through two hydroxyimino nitrogen atoms, as do most of the (E,E)-dioximes. The hydrogen-bridged Ni^II complex was converted into its BF ₂ ⁺ capped anologue by the reaction with BF₃ · Et₂O. The reaction of the Cu^II complex with 2,2′-dipyridyl as an end-cap ligand gave the homotrinuclear complex. Structures for the ligand and its complexes are proposed in accordance with elemental analysis, magnetic susceptibility measurements, ¹H, ¹³C-n.m.r, IR and MS spectral data.     

Synthesis,structures, catalytic,and anticancer activities of some coordination compounds involving two new triazole derivatives

Five N-heterocyclic carboxylate-based coordination complexes, [Co(L¹)₂(H₂O)₂]·2H₂O (1), [Cd(L¹)₂(H₂O)₂]·2H₂O (2), [Co(L²)(H₂O)₃] (3), [Ni(L²)(H₂O)₃] (4), and [Cu₂(L²)₂(H₂O)₂] (5), have been synthesized and characterized by elemental analysis, IR spectroscopy, Powder X-ray diffraction, thermogravimetric analyses, and single-crystal X-ray crystallography, where HL¹ is 2-((5-amino-1H-1,2,4-triazol-3-yl)thio)acetic acid and H₂L² is 2-((5-amino-1-(carboxymethyl)-1H-1,2,4-triazol-3-yl)thio)acetic acid. In these complexes, the hydrogen bonds (H-bonds) play an important role in their packing structures. Complex 1 has nine H-bonds showing a 3-D sqc38 topology. Complex 2 has 17 H-bonds exhibiting a 3-D hxl network. Complexes 3 and 4 are isomorphic, both of which possess ten H-bonds to present a 3-D btc topology. Complex 5 with eight H-bonds forms a 2-D sq1 structure. In addition, complex 3 catalyzes the decolorization of methyl orange. Meanwhile, 1, 3, and 5 show certain anticancer activities to inhibit the growth of HepG2 cells.     

A new unsymmetrical vic-dioxime bearing salicylaldehyde 4-aminobenzoylhydrazone and its homo-and heterotrinuclear complexes with copper(II) and nickel(II) ions

A new vic-dioxime, N-{4-[[(2-hydroxyphenyl)methylene]hydrazinecarbonyl]phenyl}aminoglyoxime (H₃L), was prepared by the reaction of anti-chloroglyoxime with salicylaldehyde 4-aminobenzoylhydrazone. The reaction of H₃L with Cu(II) salts and an appropriate simple ligand gave only homotrinuclear complexes [Cu₃(HL)₂X₂], whereas the reaction of H₃L with Ni(II) salts gave mono-and homotrinuclear complexes [Ni(H₂L)₂ and Ni₃(HL)₂X₂]. Also, heterotrinuclear complexes of H₃L were prepared by the reaction of Ni(H₂L)₂ with Cu(II) salt and an appropriate simple ligand, [NiCu₂(HL)₂X₂], X = Cl⁻, NO ₃ ⁻ , SCN⁻, CN⁻, and N ₃ ⁻ . The new vic-dioxime and its complexes were identified by elemental analyses, IR, ¹H NMR, UV-VIS, magnetic susceptibility, and mass spectral data. The elemental analyses and spectral data indicated that the hydrazone side of H₃L acted as monobasic tridentate and the fourth position was occupied by simple ligands, such as Cl⁻, NO ₃ ⁻ , SCN⁻, CN⁻, and N ₃ ⁻ . The text was submitted by the author in English.     

1-[18F]Fluoroethyleneglycol-2-nitroimidazoles, a new class of potential hypoxia PET markers

Summary 1-[2-(2-Fluoroethoxy)ethyl]-2-1H-nitroimidazole (3a), 1-{2-[2-(2-fluoroethoxy)ethoxy]ethyl}-2-1H-nitroimidazole (3b) and 1-(2-{2-[2-(2-fluoroethoxy)ethoxy]ethoxy}ethyl)-2-1H-nitroimidazole (3c) were synthesized in a two step sequence.Coupling the ditosylate of di-, tri- or tetraethylene glycol with 2-nitroimidazole followed by fluoride substitution afforded the reference compounds in high yield and¹⁸F labeling gave the corresponding markers in 70-82% radiochemical yield.     

Synthesis and Characterization of Two vic-Dioximes Containing the 1,3-Dioxolane Ring and 1,4-Diaminobutane and Their Cobalt(II), Nickel(II), Copper(II) and Zinc(II) Metal Complexes

Two new vic-dioxime ligands, (E,E)-N-{4-[(1,4-dioxaspiro[4.4]non-2-ylmethyl)amino]butyl}-N-hydroxy-2-(hydroxyimino)ethanimidamide (L¹H₂) and (E,E)-N-{4-[(1,4-dioxaspiro[4.5]dec-2-ylmethyl)amino]butyl}-N-hydroxy-2-(hydroxyimino)ethanimidamide (L²H₂) containing two different heteroatoms (N,O) have been prepared from anti-chloroglyoxime, N-(1,4-dioxaspiro[4.4]non-2-ylmethyl)butane-1,4-diamine (3) and N-(1,4-dioxaspiro[4.5]dec-2-ylmethyl)butane-1,4-diamine (4). Co^II, Ni^II and Cu^II complexes of the ligands have a metal:ligand ratio of 1:2 and the ligands coordinate through the two N atoms, as do most of the vic-dioximes. However, Zn^II complexes of the ligands have a metal:ligand ratio of 1:1 and the ligands are coordinated only by the N, O atoms of the vic-dioximes. In the Co^II complexes two water molecules, and in the Zn^II complexes a chloride ion and a water molecule, are also coordinated to the metal ion. The structures of the compounds were determined by a combination of elemental analysis, magnetic moments, molar conductances, thermogravimetric analysis (t.g.a.) and spectroscopic (u.v.–vis., i.r., ¹H- and ¹³C-n.m.r.) data.