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.     

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.     

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.     

Synthesis and Characterization of a New Dioxime and Its Heterotrinuclear BF2 + Capped Complexes

ω‐Isonitrosoacetophenone 1 Uçan, H. ? and Mirzao?lu, R. 1990. Synth. React. Inorg. Met.‐Org. Chem., 20: 437[Taylor & Francis Online], [Web of Science ®] , [Google Scholar], phenylglyoxime 2 Burakevich, J. V., Lore, A. M. and Volpp, G. P. 1971. J. Org. Chem., 36: 1[Crossref], [Web of Science ®] , [Google Scholar], chlorophenylglyoxime 1 Uçan, H. ? and Mirzao?lu, R. 1990. Synth. React. Inorg. Met.‐Org. Chem., 20: 437[Taylor & Francis Online], [Web of Science ®] , [Google Scholar], dopaminophenylglyoxime 3 Uysal, ?., Co?kun, A., Koç, Z. E., Uçan, M. and Uçan, H. ?. 2007. R. J. Coord. Chem., 33: 351–357. [Crossref] , [Google Scholar] and [(salen/saloph)Fe]₂O 4 Kopel, P., Sindelar, Z. and Klicka, R. 1998. Trans. Met. Chem., 23: 139[Web of Science ®] , [Google Scholar] have been synthesized as described in the literature procedure. [Fe(III)(salen/saloph)dopaminophenylglyoxime)] (starting complexes) have been synthesized from dopaminophenylglyoxime and tetradentate schiff bases which contain dinuclear Fe(III) oxygen‐bridges N,N′‐bis(salicylidene)ethylenediamine (salenH₂) and bis(salicylidene)‐o‐phenylenediamine (salophH₂). The new heterotrinuclear complexes have been obtained from starting complexes and Co(II), Ni(II), Cu(II) salts. Then, heterotrinuclear vic‐dioxime complexes containing BF₂ ⁺ capped have been synthesized. The complexes have been characterized as low‐spin distorted octahedral Fe(III) bridged by o‐hydroxyphenolic groups. The o‐hydroxyphenolic groups play a role as bridges for weak antiferromagnetic intramolecular exchange. The structure of dioxime and its complexes were identified by using elemental analysis, ICP‐AES, ¹H‐NMR and IR spectral data.     

以反丁烯二酰氯桥联的10,15,20-三（对-氯代苯基）卟啉二联体及其配合物的合成与性质研究

用5-（对-羟基苯基）-10,15,20-三（对-氯代苯基）卟啉为原料合成了以反丁烯二酰氯桥连的10,15,20-三（对-氯代苯基）卟啉二联体及其Zn,Cu,Co,Mn配合物,并用红外光谱、拉曼光谱、紫外光谱、质谱、核磁共振谱对其结构进行了表征.利用分子荧光光谱和表面光电压对其光学性质进行了研究.     

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 BF ₂ ⁺ -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.     

Tris(dimethylamino)phosphine Selenide Complexes of Cadmium(II): Synthesis and Multinuclear (31P, 77Se,and 113Cd) NMR Characterization in Solution

The complexes CdL₄(ClO₄)₂ (1), CdL₂(NO₃)₂ (2), and CdL₂Cl₂ (3) (L = (Me₂N)₃P(Se)) have been prepared and characterized by elemental analysis, conductivity measurements, IR, and multinuclear (³¹P, ⁷⁷Se, and ¹¹³Cd) NMR spectroscopy. ³¹P and ⁷⁷Se NMR data were informative of changes associated with complex formation. The structure of the prepared complexes was further confirmed in solution by their ¹¹³Cd NMR spectra, which show a quintuplet for the perchlorate complex and a triplet for each of the nitrate and chloride complexes due, respectively, to coupling with four and two equivalent phosphorus atoms, consistent with a four coordinate tetrahedral geometry for the cadmium center. The NMR data are discussed and compared with those reported for related complexes.     

Synthesis,spectroscopy, electrochemistry,and molecular structure of tetrakis{(E)-2-((pyridin-2-ylimino)methyl)phenolato}(hydroxido)0.5(nitrato)1.5-tetracopper(II) nitrate hydroxide

Abstract

Reaction between (E)-2-((pyridin-2-ylimino)methyl)phenol (HL) and copper(II) nitrate provides tetrakis{(E)-2-((pyridin-2-ylimino)methyl)phenolato}(hydroxido)_0.5(nitrato)_1.5-tetracopper(II) nitrate hydroxide, [(CuL)₄(NO₃)_1.5(OH)_0.5](NO₃)(OH) (1 (a) J. Miao, Z. Zhao, H. Chen, D. Wang, Y. Nie. Acta Cryst., E65, m904 (2009); (b) A. Castineiras, J.A. Castro, M.L. Duran, J.A. Garcia-Vazquez, A. Macias, J. Romero, A. Sousa. Polyhedron, 8, 2543 (1989); (c) I.S. Vasil'chenko, A.S. Antsyshkina, D.A. Garnovskii, G.G. Sadikov, M.A. Porai-Koshits, S.G. Sigeikin, A.D. Garnovskii. Koord. Khimiya, 20, 824 (1994).[Crossref], [Web of Science ®] , [Google Scholar], [Google Scholar], [Google Scholar]). ESI-mass spectra show the ion peaks for the dinuclear species at m/z 565 for [(CuL)₂(HCO₂)]⁺ and 521 for [(CuL)₂+H]⁺ and the mononuclear species at m/z 260 for [(CuL)]⁺. Vibrational spectra show very strong bands at 1604/1546?cm^?1 for ν(C?=?N/C?=?C) and at 1384, 1351?cm^?1 for ν(NO₃^–). Cyclic voltammograms demonstrate an irreversible redox processes for the Cu(II)/Cu(I) and Cu(I)/Cu(0) couples in acetonitrile. X-ray molecular structure determination explores the formation of a cationic tetranuclear copper(II)-complex, in which a deprotonated ligand molecule chelates to one copper ion with the phenolate-O and imino-N atoms. In addition, a phenolate-O atom bridges between two neighboring copper ions and a pyridine-N atom coordinates to a third copper ion, so that each ligand bridges among three copper ions in a κ²N,O:κO:κN' coordination sphere. Thus, the four copper ions and four chelating-bridging ligands assemble primarily into a cationic [(CuL)₄]⁴⁺ complex. The two copper ions are further coordinated by either a nitrate anion (75% occupancy) or a hydroxide anion (25% occupancy) and form the core of a tetranuclear [(CuL)₄(NO₃)_1.5(OH)_0.5]²⁺ cation.     

Bis(Tetramethylselenophosphoramidoyl) Methylamine Complexes of Cd(Ii) and Zn(Ii): Synthesis and Multinuclear (31P, 77Se,and 113Cd) Nmr Characterization in Solution

Abstract

Five new complexes ZnL₂(ClO₄)₂ (1), CdL₂(ClO₄)₂ (2), CdL₂(BF₄)₂ (3), CdLCl₂ (4), and CdL(NO₃)₂ (5) [L = ((Me₂N)₂PSe)₂NMe] have been synthesized and characterized by elemental analysis, infrared (IR) and multinuclear (³¹P, ⁷⁷Se, and ¹¹³Cd), and nuclear magnetic resonance (NMR) spectroscopy. The ³¹P and ⁷⁷Se NMR data showed that the title ligand is coordinated in a bidentate fashion to the metal center via its both P=Se groups. The solution structure of the cadmium complexes was further confirmed by its ¹¹³Cd NMR spectra, which displayed a quintuplet for the perchlorate complex and a triplet for each of the nitrate and chloride complexes, respectively due to coupling with four (two ligands) and two (one ligand) equivalent phosphorus nuclei, consistent with a four-coordinate tetrahedral geometry for the cadmium center. The results are discussed and compared with the corresponding oxo and thio analogues.     

一种新型含三苯胺的喹啉衍生物及其金属配合物的合成与表征

A new 8-hydroxyquinoline derivative(5)was synthesized and characterized by ESI-MS,~1H NMR spectroscopy,elemental analysis and IR spectroscopy.The photophysical properties of compounds 5,6 and 7 were also deteminedby UV-vis and FL spectroscopy.The vibrational frequency of ligand 5 predicted by using B3LYP method is in goodagreement with experimentally determined values.The compositions of the corresponding copper(Ⅱ)and zinc(Ⅱ)complexes were confirmed to be Cu(C_(29)H_(21)N_2O)_2·H_2O(6)and Zn(C_(29)H_(21)N_2O)_2·H_2O(7)by elementary analysis,thermogravimetry analysis and IR spectroscopy.     

新型含N-杂环卡宾二硫化碳配体的锰铼金属双核化合物的合成、表征及电化学性质简

合成了一系列含N-杂环卡宾二硫化碳加合物配体的锰铼金属有机化合物,其中包括3种单核化合物和3种双核化合物,对它们的结构进行了表征,并研究其反应性和电化学性质. 与三烷基膦二硫化碳配体相比,含N-杂环卡宾二硫化碳加合物配体的锰铼金属有机化合物展现出不同的反应特性. 研究结果表明,[MnRe(CO)6(μ-H){μ-CH3SC(S)IMes2}]配合物具有催化质子还原成氢气的能力.     

基于苯基修饰策略的新型可溶液加工红光铱配合物的设计、合成及电致发光性能研究

利用向环金属配体的C-Ir键的对位进行苯基取代这一结构修饰策略,成功合成了两种新型铱（III）配合物（3PhNbt）₂Ir（acac）和（3OMePhNbt）₂Ir（acac）.相较其橙光发射的母体化合物（Nbt）₂Ir（acac）,两个目标化合物的抗结晶性、非晶态热稳定性及溶解性均有显著提高,其磷光发射带也发生了5~10 nm的红移.以（3PhNbt）₂Ir（acac）和（3OMePhNbt）₂Ir（acac）为发光客体材料所制备的单层溶液加工电致红光器件,其最大发光亮度分别为1830 cd·m^-2和6630 cd·m^-2,最大电流效率分别为2.4 cd·A^-1和8.7 cd·A^-1,CIE1931色坐标分别为（0.61,0.39）和（0.62,0.38）.相比之下,以母体化合物（Nbt）₂Ir（acac）为发光客体材料所制备的参比器件,其最大发光亮度则为1620 cd·m^-2,最大电流效率仅为1.5 cd·A^-1,CIE1931色坐标为（0.59,0.41）.上述研究结果表明：向C-Ir键对位进行苯基修饰可以在提高铱（III）配合物的可溶液加工性能的同时,获得更为红移的电致发光波长,是一种简单而有效的红光铱（III）配合物的分子设计策略.     

Synthesis, Characterization and Thermal Studies of Some Iron(III) Complexes of o-Vanillin Oxime

Iron(III) complexes of o-vanillin oxime have been synthesized and characterized by different physicochemical techniques. The complexes containing thiocyanate, iodide and sulphate ionshave been subjected to non-isothermal decomposition studies in N₂ using TGand DTG techniques. The kinetic parameters for both stages of decomposition of these complexes were evaluated by weighted least-squares method using the general approach as well as the Coats–Redfern and Horowitz–Metzger equations. The results indicate that the values of kinetic parameters obtained by these three different approaches agree well. This revised version was published online in July 2006 with corrections to the Cover Date.     

Tris(dialkylamino)phosphine Chalcogenide Complexes of Tin(IV) Chloride: A Multinuclear (31P, 77Se,and 119Sn) NMR Characterization

Abstract

Four octahedral complexes of the type SnCl₄.2L [L = (R₂N)₃P(E): E = Se; R = Me(1), Et(2) and E = S; R = Me(3), Et(4)] have been studied in solution by multinuclear (³¹P, ⁷⁷Se, and ¹¹⁹Sn) NMR spectroscopy. ³¹P and ⁷⁷Se NMR data were informative of changes associated with complex formation. The solution structure of the complexes was confirmed by their ¹¹⁹Sn NMR spectra that showed two triplet features for each complex, attributed to a mixture of the expected cis and trans isomers. The triplet signal is due to the coupling with two equivalent phosphorus atoms, consistent with an octahedral geometry around the tin center. In addition, density functional theory (DFT)/B3LYP calculations have been carried out to support the interpretations of NMR data. The results are discussed and compared with those reported for related complexes.

GRAPHICAL ABSTRACT