Synthesis,Structures and Properties of Four Coordination Polymers Constructed from 5‐Nitroisophthalate and Benzimidazole Ligand

Four coordination polymers, [Cu(NIPH)(Bim)₂]_n ( 1 ), [Co(NIPH)(Bim)₂]_n ( 2 ), [Zn(NIPH)(Bim)]_n ( 3 ), and [Cd(NIPH)(Bim)(H₂O)]_n ( 4 ) (NIPH = 5‐nitroisophthalate and Bim = benzimidazole) have been synthesized and characterized by elemental analysis, IR, TGA and single‐crystal X‐ray diffraction. The crystal structural analyses reveal that 1 and 2 are composed of zig‐zag chains and straight line chains, respectively. 3 and 4 are constructed by double‐stranded loop‐like chains. All these chain‐like structures are finally packed into three‐dimensional networks through hydrogen bonds. Thermogravimetic analyses (TGA) of 1 – 4 and temperature‐dependent magnetic susceptibilities of 1 have been performed.     

Facile one-pot synthesis of functionalized organophosphonate esters via ketone insertion into bulky arylphosphites

The reaction of phosphorus trichloride with 2,6-diisopropyl phenol in the presence of LiCl under reflux conditions for 24 h produces a mixture of (ArO)PCl₂ and (ArO)₂PCl (Ar = 2,6-iPr₂C₆H₃). The hydrolysis of the aryloxy compounds in acetone/H₂O results in the formation of two novel phosphonate ester derivatives [(ArO)P(O)(OH)(CMe₂OH)] (1) and [(ArO)₂P(O)(CMe₂OH)] (2), respectively in a moderate yield. The title compounds have presumably formed via acetone insertion to the P-H bonds of (ArO)P(O)(H)(OH) and (ArO)₂P(O)(H), respectively, in the presence of HCl produced during the hydrolysis. Compounds 1 and 2 have been characterized by elemental analysis, and ESI-mass, Infrared and NMR spectroscopic techniques. Further, solid state structures of 1 and 2 have been established by single crystals X-ray diffraction studies.     

Synthesis and characterization of modular polyphosphonate homopolymers and copolymers

Linear polyphosphonates with the generic formula –[P(Ph)(X)OR′O]_n– (X = S or Se) have been synthesized by polycondensations of P(Ph)(NEt₂)₂ and a diol (HOR′OH = 1,4-cyclohexanedimethanol, 1,4-benzenedimethanol, tetraethylene glycol, or 1,12-dodecanediol) followed by reaction with a chalcogen. Random copolymers have been synthesized by polycondensations of P(Ph)(NEt₂)₂ and mixture of two of the diols in a 2:1:1 mol ratio followed by reaction with a chalcogen. Block copolymers with the generic formula –[P(Ph)(X)OR′O]_{(x + 2)} –[P(Ph)(X)OR′O]_{(x + 3)}– (X = S or Se) have been synthesized by the polycondensations of Et₂N[P(Ph)(X)OR′O]_{(x + 2)}P(Ph)NEt₂ oligomers with HOR′O[P(Ph)(X)OR′O]_{(x + 3)}H oligomers followed by reaction with a chalcogen. The Et₂N[P(Ph)(X)OR′O]_{(x + 2)}P(Ph)NEt₂ oligomers are prepared by the reaction of an excess of P(Ph)(NEt₂)₂ with a diol while the HOR′O[P(Ph)(X)OR′O]_{(x + 3)}H oligomers are prepared by the reaction of P(Ph)(NEt₂)₂ with an excess of the diol. In each case the excess, x is the same and determines the average block sizes. All of the polymers were characterized using ¹H, ¹³C{¹H}, and ³¹P{¹H} NMR spectroscopy, TGA, DSC, and SEC. ³¹P{¹H} NMR spectroscopy demonstrates that the random and block copolymers have the expected arrangements of monomers and, in the case of block copolymers, verifies the block sizes. All polymers are thermally stable up to ~300°C, and the arrangements of monomers in the copolymers (block vs. random) affect their degradation temperatures and T_g profiles. The polymers have weight average MWs of up to 3.8 × 10⁴ Da.     

Syntheses,crystal structures,and luminescence of carboxylato-bridged coordination compounds

Two 2-D metal carboxylate coordination compounds [Tb(pydc)(ox)_1/2(H₂O)₂] (1) and [Cd(pydc)(me)(H₂O)]₂ · H₂O (2) (pyridine-2,5-dicarboxylic acid = pydc, oxalic acid = ox, me = methanol) have been synthesized under hydrothermal conditions. Carboxylates are building blocks in the formation of zigzag chain and cockle stair-like chain structures for 1 and 2, respectively. Both the compounds have been structurally determined by single-crystal X-ray diffraction, and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and fluorescence spectra.     

Ir(I)–carbonyl complexes of coumarinazoimidazoles: Synthesis structure, electrochemistry, photophysical properties and DFT calculations

The reactions of Vaska’s complex [IrCl(CO)(PPh₃)₂] with 2-(coumaryl-6-azo)imidazole (CZ-H) and its derivatives (CZ-X) have synthesized [Ir(CZ)(CO)(PPh₃)₂] and [Ir(CZ-X)(CO)(PPh₃)₂]. All the complexes have been characterized by FT-IR, UV-Vis, ¹H NMR and FAB-MS spectroscopy. The structural confirmation has been done in one case, by a single crystal X-ray diffraction study, which shows a distorted square pyramidal geometry around the central Ir atom. The complexes are emissive at room temperature. The cyclic voltammetry of the complexes shows a metal centered irreversible oxidation and ligand centered quasireversible reduction couples. To get an insight into the electronic structure, absorption spectra and electrochemical properties, detailed calculations on all three complexes have been performed at the DFT level.     

Synthesis,structure, and DNA-binding properties of manganese(II) and nickel(II) complexes with tris(N-ethylbenzimidazol-2-ylmethyl)amine ligand

Tris(N-ethylbenzimidazol-2-ylmethyl)amine (Etntb), [Mn(Etntb)(DMF)(H₂O)](pic)₂ (1), and [Ni(Etntb)(DMF)(H₂O)](pic)₂ (2) (pic?=?picrate) have been synthesized and characterized by elemental analyses, molar conductivities, UV–Visible spectra, and IR spectra. Single-crystal X-ray diffraction revealed that the complexes have the same arrangement with distorted octahedral coordination geometries. DNA-binding properties of the free ligand, 1, and 2 have been investigated by electronic absorption, fluorescence, and viscosity measurements. The results suggest that the ligand and its complexes bind DNA via intercalation, and their binding affinity for DNA follows the order 2?>?1?> ligand.     

Nitrosyl rhenium complexes: Syntheses,properties, and structures of acetylacetonato derivatives

Some new complexes of rhenium containing monocoordinating acetylacetone viz. [Re(NO)(acac)₂(Cl)H₂O], Re(NO)(acac)₃(acacH)(H₂O)₂ have been synthesized by reacting acetylacetone with either Re(NO)Cl₃ · H₂O or Re(NO)(OH)₃ · H₂O. The preparation of [Re(NO)(py)(acac)₂(Cl) · H₂O], [Re(NO)(acac)(OH)(Cl) · H₂O], [Re₂(NO)₂(acacH)₃(acac)₂ · Cl₄], [Re(NO)(acac)₂(OH) · H₂O] · 2 H₂O have also been described. These complexes were characterized through their elemental analyses, u.v., vis, i.r., ¹Hn.m.r., magnetic, and conductance data.     

Synthesis, crystal structures and fluorescence properties of four mixed-ligands Zn(Ⅱ) and Cd(Ⅱ) coordination compounds

Four new coordination compounds, [Zn(dba)(bpy)]n (1), {[Zn(dba)(phen)]·2H2O}n (2), [Cd(dba)(bpy)(H2O)2] (3) and [Cd2(dba)2(phen)2]n (4) (H2dba = 2,5-dihydroxy-p-benzenediacetic acid, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline) have been prepared via solvothermal method and characterized by sin-gle-crystal X-ray diffraction, infrared spectroscopy, elemental analysis and powder X-ray diffraction. 1 and 2 possess 1D infinite chain structures. Complex 3 exhibits a mononuclear structure. Complex 4 owns bi...     

Oxorhenium complexes with the 8-quinolinolato ligand. X-ray structure and DFT calculations for [ReOX2(hqn)(AsPh3)] and [ReOX2(hqn)(PPh3)] complexes

The reactions of [ReOX₃(AsPh₃)₂] and [ReOX₃(PPh₃)₂] with 8-hydroxyquinoline (Hhqn) have been examined and the complexes [ReOX₂(hqn)(AsPh₃)] and [ReOX₂(hqn)(PPh₃)] (X = Cl, Br) have been obtained, respectively. The crystal and molecular structures of [ReOCl₂(hqn)(AsPh₃)] (1) and [ReOBr₂(hqn)(PPh₃)] (4) have been determined. The electronic structure of 1 has been calculated with the density functional theory (DFT) method. The spin-allowed electronic transitions of 1 have been calculated with the time-dependent DFT method, and the UV–Vis spectrum of [ReOCl₂(hqn)(AsPh₃)] has been discussed on this basis.     

Synthesis,spectroscopic investigation,structural characterization and DFT calculation of the complexes [ReX2(N2COPh)(4-PhPyr)(PPh3)2] (X = Cl, Br)

The reactions of [ReX₂(η²-N₂COPh-N′,O)(PPh₃)₂] with 4-phenylpyrimidine have been performed. As a result, the two complexes [ReX₂(N₂COPh)(4-PhPyr)(PPh₃)₂] (X = Cl, Br) (4-PhPyr = 4-phenylpyrimidine), isostructural in the solid state, have been obtained. The crystal and molecular structures of ([ReCl₂(N₂COPh)(4-PhPyr)(PPh₃)₂])₂·CHCl₃ (1) and ([ReBr₂(N₂COPh)(4-PhPyr)(PPh₃)₂])₂·CHCl₃ (2) have been determined. The electronic structure of [ReCl₂(N₂COPh)(4-PhPyr)(PPh₃)₂] has been examined using the density functional theory (DFT) method. The spin-allowed electronic transitions of 1 have been calculated with the time-dependent DFT method, and the UV–Vis spectrum of [ReCl₂(N₂COPh)(4-PhPyr)(PPh₃)₂] has been discussed on this basis.     

以2-(1-吡唑基甲基)吡啶类化合物为配体的羰基钼、钨衍生物的合成及结构

合成了2-[1-(3-叔丁基)吡唑基甲基]吡啶(CH2(Py)(3-ButPz)),并研究了羰基钼(钨)与该配体及其类似物2-(1-吡唑基甲基)吡啶(CH2(Py)(Pz))和2-[1-(3,5-二甲基)吡唑基甲基]吡啶(CH2(Py)(3,5-Me2Pz))的反应,合成了6个含双齿螯合的2-(1-吡唑基甲基)吡啶类配体的四羰基金属衍生物CH2(Py)(3-ButPz)M(CO)4,CH2(Py)(Pz)M(CO)4和CH2(Py)(3,5-Me2Pz)M(CO)4(M=Mo或W)。当用SnCl4处理CH2(Py)(3,5-Me2Pz)M(CO)4时,Sn-Cl键对金属中心发生氧化加成得到2个杂双核金属有机化合物CH2(Py)(3,5-Me2Pz)M(CO)3(Cl)SnCl3。所有新化合物均通过了红外和核磁的表征,CH2(Py)(3-ButPz)W(CO)4和CH2(Py)(3,5-Me2Pz)W(CO)3(Cl)SnCl3的结构还得到了X-射线单晶衍射的确证。用循环伏安法测定了四羰基金属衍生物的电化学性质。     

New oxorhenium complexes with 2-(2′-hydroxyphenyl)-2-benzoxazolinato ligand. X-ray structure and DFT calculations for [ReOX2(hbo)(AsPh3)] and [ReOX2(hbo)(PPh3)] complexes

The reactions of [ReOX₃(AsPh₃)₂] and [ReOX₃(PPh₃)₂] with 2-(2′-hydroxyphenyl)-2-benzoxazoline (Hhbo) have been examined and [ReOX₂(hbo)(AsPh₃)] and [ReOX₂(hbo)(PPh₃)] (X = Cl, Br) complexes have been obtained. The crystal and molecular structures of [ReOCl₂(hbo)(AsPh₃)] (1) and [ReOBr₂(hbo)(PPh₃)] (4) have been determined. The electronic structures of 1 and 4 have been calculated with the density functional theory (DFT) method. The spin-allowed electronic transitions of 1 and 4 have been calculated with the time-dependent DFT method, and the UV–Vis spectra of these complexes have been discussed.     

Synthesis of Ir Catalysts Featuring Amide-functionalized NHC Ligands and Survey of their Activity on Formic Acid Dehydrogenation

2 a and 2 b , [Ir(CI)(COD)(NHC)] (COD=1,5-cyclooctadiene), have been prepared via transmetallation from NHC−Ag complexes. [Rh(CI)(COD)(NHC)] ( 4 ) was prepared analogously. [Ir({κ-C,N-(NHC-acetamide−1H)}(COD)] ( 3 c ) has been synthesized via transmetallation from the deprotonated NHC−Ag complex. [IrCp*({κ-C,N-(NHC-acetamide−1H)}] ( 5 ) (Cp*=pentamethylcyclopentadienyl), has been obtained analogously. [Ir(CI)(CO)₂(NHC)] ( 6 ) and [Ir({κ-C,N-(NHC-acetamide−1H)}(CO)₂] ( 7 ) have been prepared by carbonylation of 2 b and 3 c , respectively. The catalytic activity of these complexes has been evaluated in the dehydrogenation of formic acid, under solventless conditions, in the presence of water as a cosolvent, and in a 5 : 2 HCOOH/Et₃N mixture, with the best TOF values being obtained in the case of the latter. Stoichiometric experiments suggest COD hydrogenation as the preactivation step.     

Synthesis,characterization, and biological evaluation of Cu(II) complexes with the proton transfer salt of 2,6-pyridinedicarboxylic acid and 2-amino-4-methylpyridine

A proton transfer compound, (Hamp)⁺(Hdipic)^??·?1.5H₂O (1), and Cu(II) complexes, [Cu(dipic)(amp)(H₂O)]?·?[Cu(dipic)(amp)]?·?H₂O?·?CH₃COOH (2) and [Cu(dipic)(amp)Cu(dipic)(amp)(H₂O)Cu(dipic)(amp)(H₂O)]?·?3H₂O (3), have been synthesized from 2,6-pyridinedicarboxylic acid (H₂dipic) and 2-amino-4-methylpyridine (amp). They have been characterized by elemental, spectral (¹H-NMR, IR, and UV-Vis), and thermal analyses. In addition, magnetic measurements and single crystal X-ray diffraction have been applied to 2 and 3. The crystal structure of 2 consists of two independent and different cationic sites with Cu²⁺ ions. Cu1 is four-coordinate in a distorted square planar geometry and Cu2 is five-coordinate in a distorted square pyramid. Compound 3 has three independent and different cationic sites of Cu²⁺ ions. Cu1 is four-coordinate in a distorted square planar geometry and Cu2 and Cu3 have five-coordinate, distorted square-pyramidal sites. Inhibitory effects of 1, 2, and 3 have been studied and compared with starting compounds (amp and H₂dipic) on bacterial growth of Staphylococcus aureus and Escherichia coli cultures. Compounds 2 and 3 prevent bacterial growth although 1 has no effect. Compounds 2 and 3 are more effective than amp and H₂dipic, at similar concentrations on preventing bacterial growth for both organisms.     

Biological Activity of Flavonoids Copper Complexes

Three flavonoid copper(II) complexes Cu₂(quercetin)(CH₃COO)₃(CH₃OH) ( 1 ), Cu(anthrarufin)(CH₃COO)·1/2H₂O ( 2 ) and Cu(naringin)(OCH₃)(CH₃OH)₂ ( 3 ) have been synthesized and characterized by elemental analysis, IR, electronic absorption and EPR (X‐band) spectroscopy. The complexes have a strong protective action over the Δsod1 mutant of S. cerevisiae against reactive oxygen radicals generated by an external source of free radicals (H₂O₂ or the superoxide‐generating, menadione). On the other hand, the complexes cleave DNA efficiently even in the absence of reducing agents. The main reactive oxygen species responsible for the DNA strand cleavage have been determined using radical scavengers. A probably mechanism of the DNA damage is proposed.     

1-(2′-Pyridylazo)-2-naphtholate complexes of ruthenium: Synthesis,characterization, and DNA binding properties

Reaction of 1-(2′-pyridylazo)-2-naphthol (Hpan) with [Ru(dmso)₄Cl₂] (dmso = dimethylsulfoxide), [Ru(trpy)Cl₃] (trpy = 2,2′,2″-terpyridine), [Ru(bpy)Cl₃] (bpy = 2,2′-bipyridine) and [Ru(PPh₃)₃Cl₂] in refluxing ethanol in the presence of a base (NEt₃) affords, respectively, the [Ru(pan)₂], [Ru(trpy)(pan)]⁺ (isolated as perchlorate salt), [Ru(bpy)(pan)Cl] and [Ru(PPh₃)₂(pan)Cl] complexes. Structures of these four complexes have been determined by X-ray crystallography. In each of these complexes, the pan ligand is coordinated to the metal center as a monoanionic tridentate N,N,O-donor. Reaction of the [Ru(bpy)(pan)Cl] complex with pyridine (py) and 4-picoline (pic) in the presence of silver ion has yielded the [Ru(bpy)(pan)(py)]⁺ and [Ru(bpy)(pan)(pic)]⁺ complexes (isolated as perchlorate salts), respectively. All the complexes are diamagnetic (low-spin d⁶, S = 0) and show characteristic ¹H NMR signals and intense MLCT transitions in the visible region. Cyclic voltammetry on all the complexes shows a Ru(II)–Ru(III) oxidation on the positive side of SCE. Except in the [Ru(pan)₂] complex, a second oxidative response has been observed in the other five complexes. Reductions of the coordinated ligands have also been observed on the negative side of SCE. The [Ru(trpy)(pan)]ClO₄, [Ru(bpy)(pan)(py)]ClO₄ and [Ru(bpy)(pan)(pic)]ClO₄ complexes have been observed to bind to DNA, but they have not been able to cleave super-coiled DNA on UV irradiation.     

Ligand-directed assembly of distinct 1-D CdII coordination polymers with a bent dipyridyl derivative and two isophthalates bearing different 5-substituents

Two 1-D Cd^II coordination polymers, {[Cd(4-abpt)(hip)(H₂O)₂](H₂O)_7/2} _n (1) and {[Cd(4-Habpt)(sip)(H₂O)](H₂O)₂} _n (2) (4-abpt?=?4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole, H₂hip?=?5-hydroxyisophthalic acid, H₃sip?=?5-sulfoisophthalic acid), have been hydrothermally synthesized and structurally characterized. Complex 1 has a comb-like 1-D coordination chain, while 2 presents a 1-D dual-track motif. The structural modulation of the coordination polymers can be achieved by simply changing the 5-substituent of the isophthalate from a hydroxyl group to a sulfonate group. Further, supramolecular architectures with higher dimensionality are constructed via hydrogen bonding and/or aromatic π-stacking interactions. Both complexes have been characterized by IR, microanalysis, and powder X-ray diffraction techniques. In addition, the solid fluorescence properties of both complexes have also been investigated.     

两个双四唑胺的铜配合物的合成、结构及荧光性质(英文)

用Demko-Sharpless方法自制的双四唑胺配体,再混以乙二胺和丙二胺螯合配体,合成了2个新颖的铜的配合物Cu(bta)(en)(H2O)(1)与Cu(bta)(1,3-pda)(H2O)(2)。X-射线单晶衍射表征了2个配合物的结构。2个配合物的水溶液都表现出了双四唑胺配体的特征吸收波长与荧光发射波长。     

Basicity of transiton metal carbonyl complexes : XIII. Reactions of the π-cyclopentadienyl complexes of molybdenum and tungsten with aprotic acids

The aprotic acids HgCl₂ and SnX₄ (X  Cl, Br) react with the π-complexes C₅H₅M(CO)(NO)(L) (II, M  Mo W; L  PPh₃) by attack at the metal center. With HgCl₂ complexes II yield stable neutral 1:1 adducts CpM(CO)(NO)(L)HgCl₂(III). In the case of SnCl₄, complexes II initially produce the ionic 1:2 adducts [CpM(CO)(NO)(L)(SnCl₃)]⁺SnCl₅^-(IV) which, as a result of oxidative elimination of CO, turn into the neutral complexes CpM(NO)(L)(SnCl₃)(Cl)(V). In reactions of II with SnBr₄ the corresponding CpM(NO)(L)(SnB₃)(Br) complexes are formed directly. The formation of III–V is accompanied by a considerable increase of the frequencies ν(CO) and ν(NO). The structures of the complexes IV (M  Mo) and V (M  Mo) have been established by an X-ray structure analysis.     

Synthesis, structure and catalytic activity of the first iridium(I) siloxide versus chloride complexes with 1,3-mesitylimidazolin-2-ylidene ligand

The first iridium(I) complex containing siloxyl and N-heterocyclic carbene ligand such as [Ir(cod)(IMes)(OSiMe₃)] (1) and [Ir(CO)₂(IMes)(OSiMe₃)] (3) have been synthesized and their structures solved by spectroscopy and X-ray methods as well as catalytic properties in selected hydrogenation reactions have been presented in comparison to their chloride analogues, i.e. [Ir(Cl)(cod)(IMes)] (2) and [Ir(Cl)(CO)₂(IMes)] (4). The attempts at synthesis of iridium(I) complex with tert-butoxyl ligand has failed as leading instead to the iridium hydroxide complex [Ir(cod)(OH)(IMes)] (5) whose X-ray structure has also been solved. All complexes (1)-(5) show square planar geometry typical of the four-coordinated iridium complexes. Catalytic activity of complexes 1 and 2 was tested in transfer hydrogenation of acetophenone and hydrogenation of olefins.