Synthesis and Characterization of a New (E, E)-Dioxime and Its Homo and Heteronuclear Complexes Containing Macrobicylic Moieties

A new N,N'-substituted diaminoglyoxime (H ₂ L) containing a diazatetraoxamacrobicycle [2.2.2_B] has been synthesized from an aromatic primary amine attached to the cryptand moiety and cyanogen-di-N-oxide. The BF₂ ⁺-capped Co(III) and heterotri-nuclear complexes of thevic-dioxime were prepared. The new compounds werecharacterized by a combination of elemental analysis and ¹H NMR,¹³C NMR, IR and MS spectral data.     

The synthesis and characterization of ( E,E )-dioxime and its transition metal complexes containing 12-membered macrocycles linked to ferrocenyl-methyl groups

13,14-bis(Hydroxyimino)-4,7-bis(ferrocenylmethyl)-2,3,4,5,6,7,8,9-octahydrobenzo[k]-4, 7-diaza-1,10-dithiacyclododecine[13,14-g]-quinoxaline (H₂L) has been prepared from (E,E)-dichloroglyoxime and 12,13-diamino-4,7-bis(ferrocenylmethyl)-2,3,4,5,6,7,8,9-octahydrobenzo[k]-4,7-diaza-1,10-dithiacyclododecine which was synthesized from 12,13-dinitro-4,7-bis(ferrocenylmethyl)-2,3,4,5,6,7,8,9-octahydrobenzo[k]4,7-diaza-1,10-dithia cyclododecine. Mononuclear nickel(II) and copper(II) complexes of H₂L have a metal-ligand ratio of 1?:?2 and the ligand coordinates through two nitrogen atoms, as do most (E,E)-dioximes. The homotrinuclear [Cu(L)₂Cu₂(dipy)₂](NO₃)₂ compound coordinates to the other two copper(II) ions through deprotonated oximate oxygens and two 2,2′-dipyridyl as an end-cap ligand to yield the trinuclear structure. The ligand and its complexes have been characterized on the basis of ¹H, ¹³C NMR, IR and MS spectroscopy and elemental analyses.     

The synthesis and characterization of a new (E,E)-dioxime containing 18-membered dithiadiazadioxamacrocyclic moieties and its mononuclear complexes

A new (E,E)-dioxime, (21Z,22Z)-6,7,9,10,12,13-hexahydro-16H- benzo[h][1,4,7,16,10,13][1, 4,7,16,10,13]dioxadithiadiazacyclooctadecine-21,22(20H,23H)-dione dioxime (H ₂ L) has been synthesized by reacting cyanogen-di-N-oxide (2) with (2-{[2-(2-{2-[(7-aminocyclohepta-1,4,6-trien-1-yl)thio]ethoxy}ethoxy)ethyl]thio}phenyl)amine. Mononuclear complexes of this ligand have been synthesized by reacting the vic-dioxime (H₂L) with CuCl₂, NiCl₂.6H₂O and CoCl₂.6H₂O respectively. The BF₂⁺ capped Ni(II) and Co(III) complexes of the dioxime have been synthesized from. The new compounds were characterized by a combination of elemental analysis, ¹H- and ¹³C-n.m.r, I.R. and m.s. spectral data.     

Solvent Extraction of Heavy Metals with a 23-Membered Macrocyclic Ionophore Attached with BF 2 + -Capped Cobalt(III) Complex

A new (E, E)-dioxime cobalt(III) complex [Co(HL)₂pyCl]containing four 23-membered macrocyclic ionophores has beenprepared. The cobalt(III) complex [Co(LBF₂)₂pyCl]bridged with BF₂ ⁺ was prepared using the precursorcobalt(III) complex and boron trifluoride ethyl ethercomplex. The solvent extraction of heavy metal cationssuch as Ni²⁺, Cu²⁺, Zn²⁺, Hg²⁺ and Pb²⁺ by the BF₂ ⁺-capped cobalt(III) complex has been investigated. The structure of the complexes is proposedaccording to elemental analyses, ¹H and ¹³C-NMR, IRand mass 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.     

Synthesis and characterization of new copperphthalocyanine carrying mixed donor macrocyclic moieties

The new phthalocyanine peripherally substituted with a twelve-membered dioxadiaza macrocycle was synthesized by cyclotetramerization of 1,2-bis(2-{4′-[(4′-methylphenyl)-sulphonyl]-1′,7′-dioxa-4′,10′-diazacyclododecane})-4,5-dicyanobenzene (4) which was obtained from 1,2-bis(2-{4′-[(4′-methylphenyl)sulphonyl]-1′,7′-dioxa-4′,10′-diazacyclododecane})-4,5-dibromobenzene (3). Metallophthalocyanine was also prepared by the reaction of the dicyano-substituted macrocycle in the presence of anhydrous CuCN. The new compounds were characterized by a combination of elemental analysis, ¹H and ¹³C?NMR, IR, electronic and mass spectroscopies.     

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.     

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 Characterization of a New (E,E)-Dioxime and its Homonuclear Complexes

N′-(4′-Benzo[15-crown-5]naphthylaminoglyoxime (H₂L) and its sodium chloride complex (H₂L·NaCl) have been prepared from 2-naphthylchloroglyoxime, 4′-aminobenzo[15-crown-5] and sodium bicarbonate or sodium bicarbonate and sodium chloride. Nickel(II), cobalt(II) and copper(II) complexes of H₂L and H₂L·NaCl have a metal–ligand ratio of 1:2 and the ligand coordinates through the two N atoms, as do most of the vic-dioximes. The BF₂⁺-capped Ni(II), Co(III) and mononuclear complexes of thevic-dioxime were prepared. The macrocyclic ligands and their transition metal complexes have been characterized on the basis of IR, ¹H NMR spectroscopy and elemental analyses data.     

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.     

Spectroscopic and electrochemical investigation with coordination stabilities: mononuclear manganese(II) complexes derived from different constituents macrocyclic ligands

Since the manganese(II) complexes are known as having a high degree of stability, some of them may be able to play a very important role in biosystems. We prepared manganese(II) complexes with different chromospheres containing macrocyclic ligands bearing N, S and O like functional donor atoms in order to obtain different models of compounds. So these new manganese(II) complexes were derived from macrocyclic ligands by chelating them with metal ions. Thus, two macrocyclic ligands, L(1): 2,4-diphenyl-1,5-diaza-8,12-dioxo-6,7:13,14-dibenzocyclo tetradeca-1,4-diene[N(2)O(2)]ane; L(2): 2,4,9,11-tetraphenyl-6,13-dimethyl-1,5,8,12-traazacyclotertr-adeca-1,4,8,11-tetraene[N(4)]ane; and two more different form first one viz.-L(3): 1,7-diaza-4-monothia-10,14-dioxo-8,9:15,16-cyclohexadecane[N(2)O(2)S]ane and L(4): 4,13-diaoxa-1,7,10,16-hexazacyclooctadecane[N(4)O(2)]ane were prepared and their capacity to retain the manganese(II) ion in solid as well as aqueous solution was determined from various physiochemical techniques viz: characterized by elemental analyses, molar conductance measurements, magnetic susceptibility measurements, mass, IR, electronic, ESR spectral studies and cyclic voltammetric measurements.     

Synthesis and characterization of a new cyclic phosph(V)azane ligand [(C6H5N)P(O)H]2 and its zinc(II) complex

The new cyclic phosph(V)azane ligand [(C₆H₅N)P(O)H]₂ (2) is obtained from the reaction between PCl₃ and PhNH₂ in toluene followed by controlled hydrolysis of the product in an H₂O–CHCl₃ solution. Compound 2 is the first example of P(V) dimer [(µ-NC₆H₅)P(H)=O]₂, a P₂N₂ ring with two P(O)H moieties. The reaction of 2 with ZnCl₂ in a molar ratio of 1?:?1 in tetrahydrofuran yields the cyclophosph(V)azane complex Cl₂Zn[(C₆H₅N)P(O)H]₂ (3) in which Zn–O bonds form directly between a cyclic phosph(V)azane ligand and Zn(II). The products have been characterized by infrared, multinuclear (¹H, ³¹P, ¹³C) NMR, mass spectrometry, and elemental analysis.     

Synthesis and characterization of binuclear manganese(IV,IV) and mononuclear cobalt(II) complexes based on 2-(2-hydroxyphenyl)-1H-benzimidazole

The bidentate benzimidazolic hpbm (1), [2-(2-hydroxyphenyl)-1H-benzimidazole], was obtained under mild conditions, and its corresponding metal complexes, di-µ-oxo dimanganese(IV,IV) [Mn₂O₂(hpbm)₄ · 2Py · 5H₂O] (2), and mononuclear complex [Co(hpbm)₂] (3), were prepared and characterized. The crystal structures of 2 and 3 have been established by X-ray diffraction. Complex 2 consists of two six-coordinate manganese(IV) coordinated to two hpbm ligands and bridged by two O^2? with a Mn–Mn distance of 2.777 Å. For 3, a Co(II) is coordinated to two deprotonated hpbm in a nearly tetrahedral environment. Hydrogen bonds play pivotal roles in constructing the dimensional structures of both the compounds.     

Cadmium(II) complexes with phosphine tellurides: synthesis and multinuclear (31P, 125Te,and 113Cd) NMR characterization in solution

New cadmium(II) complexes with phosphine telluride ligands of the type CdX₂(R₃PTe)_n [X?=?ClO₄^?, n?=?4: R?=?n-Bu (1), Me₂?N (2), C₅H₁₀?N (3), C₄H₈?N (4) or OC₄H₈?N (5); X?=?Cl^–, n?=?2: R?=?n-Bu (6), Me₂?N (7), C₅H₁₀?N (8), C₄H₈?N (9) or OC₄H₈?N (10)] have been synthesized and characterized by elemental analyses, IR and multinuclear (³¹P, ¹²⁵Te, and ¹¹³Cd) NMR spectroscopy. In particular, the solution structures of these complexes were confirmed by ¹¹³Cd NMR at low temperature, which displays a quintuplet for each of the perchlorate complexes and a triplet for each of the chloride complexes due to coupling with four and two equivalent phosphorus atoms, respectively, indicating a four-coordinate tetrahedral geometry for the metal center. These multiplet features were further accompanied by one bond Te–Cd couplings, clearly showing that the ligand is coordinated to the metal through tellurium. The results are discussed and compared with those obtained for closely related phosphine chalcogenide analogs.