二[(R-R'-环己烯基)-甲基取代茂]二氯钛和锆化合物的核磁共振和红外光谱研究

The NMR and FT\|IR Spectra of ten (ηC 6H\-9CRR′ Cp)\-2MCl\-2 (M=Ti,Zr) were measured.The constructions of the compounds were identified by 1H NMR and 13 C NMR spectra.All complexes are bonded by M\|Cp through center of Cp.The vibration modes were reasonably assigned,absorption of ν s M\|Cp (A\-1) (M=Ti and Zr) vibration all appear in 310?cm -1 or so,while ν as M\|Cp (B) appear around 410?cm -1 and 360?cm -1 for Ti and Zr respectively.The influence of the center metal atoms and the substituents upon the NMR and FT\|IR spectra were discussed.     

Ethylene tetramerization with a highly active and long-lifetime trinuclear diphenylphosphinoamine/Cr（III）/MAO catalyst

The synthesis and characterization of a novel trinuclear diphosphinoamine ligand 2 are reported. The ligand combined with Cr(III), activated with methylaluminoxane, lead to highly active and long-lifetime catalytic systems for the tetramerization of ethylene to form 1-octene. The effects of reaction temperature, reaction pressure, molar ratio of Al/Cr and bis(diphenylphosphino)amine/Cr on the catalytic activity and product selectivity were studied. Compared with its mononuclear analogue 1, ligand 2 showed a higher catalytic activity and longer lifetime for ethylene tetramerization in the presence of methylaluminoxane as cocatalyst. High molecular weight polyethylene was generated as a by-product with extremely broad molecular weight distributions.     

Recent progresses of late-transition metal complexes with nonsymmetric diimine ligands in ethylene polymerization and oligomerization

Researches of late-transition metal complexes for ethylene polymerization and oligomerization have attracted a lot of attention in the last two decades. A large number of late-transition metal complexes with symmetric diimine ligands have been extensively studied. Although the research of unsymmetric diimine late-transition metal complexes was still in the initial stage, some superior performances were observed in olefin polymerization. Recent developments in the research of ethylene poly- merization and oligomerization catalyzed by late-transition metal complexes with unsymmetric diimine ligands were summarized in this review, with the influence of complex structure on the catalytic performance of the catalyst analyzed.     

New Palladium-Imidazole and Imidazoline Complexes:Structures and Reactivity in Coupling Reaction

1 Results We have recently reported the Mizoroki-Heck reaction catalyzed by PdCl2 and imidazole ligands[1]. During the course of our study of palladium imidazole complex,we disclosed the synthesis of trans-Pd(Ln)2Cl2 by the reaction of PdCl2 with Ln (where L1=2-phenylimidazole,L2=2-phenylimidazole) in a 1∶2 molar ratio.The single crystals of trans-Pd(L1)2Cl2·2DMF (1a) and trans-Pd(L2)2Cl2 (2a) were obtained by following slow evaporation of DMF as a solvent. The single crystal of trans-Pd(L2)2Cl2 (2b) was obtained by slow diffusion of toluene into the DMF solution of complexes,Pd(L1)2Cl2 (1b) was obtained in powder by this way. The compositions of isolated complexes have been determined by elemental analyses. The molecular structures of complex 1a,2a and 2b have been characterized by single crystal X-ray analysis (Fig.1). To compare their catalytic efficiency,the coupling reactions between 4-bromotoluene and tere-butylacrylate using isolated complexes were carried out. In the present of 0.1 mol% palladium complex 1a and 1b,the coupling product were obtained with a yield of 96% after 24 hours and 97% after 12 hours,respectively. The behaviors of obtained complexes in solution based on 1H NMR analysis will be also discussed in the symposium.     

Synthesis,Structural Characterization,and Electrochemical Properties of Binuclear Copper(Ⅱ) Complexes Containing Tetradentate Schiff Base Ligand

Two binuclear copper(Ⅱ) complexes, [Cu2(saloph)2 (μ-O)2]-2(DMF)[H2saloph=N,N′-o-phenylenebis(salicylideneaminato)] (a) and [Cu2(salen)2(μ-O)2] [H2salen=N,N′-bis(salicylic-deneaminato) ethylene] (b)were synthesized and characterized by X-ray crystallography. Both of them have distorted rectangular pyramidal geometry around Cu(Ⅱ). The complete series of complexes show bridging phenoxo groups between the copper centers, together with hydroxo-bridges in these complexes. The complexes have also been characterized by elemental analysis, IR, TG-DTA, and electrochemical results.     

Synthesis and characterization of organometallic macrocyclic rhodium (Ⅲ) complex with pyrazine ligands

The synthesis and structure research of organometal-lic macrocyclic complexes has been a very active field of modern chemistry [1—3]. In this field, Pd2+, Pt2+ complexes were first used as the building block, connected by het-erocyclic ligands, to construct metal macrocyclic com-pound[4,5]. The fac-Re(CO)5X (X = Cl, Br) fragment, for example, was shown to be a versatile building block for the synthesis of metallamacrocycles[6]. Some of this kind of molecule have been found applications in…     

Crystal structures,antibacterial activity and thermal decomposition kinetics of lanthanide complexes with 4-chloro-2-methoxybenzoic acid and 1,10-phenanthroline

A series of lanthanide complexes [Ln(4-Cl-2-MOBA)3phen]2(Ln=Sm(1), Nd(2), Ho(3), Eu(4), Dy(5), and Tb(6); 4-Cl-2-MOBA=4-chloro-2-methoxybenzoate, phen=1,10-phenanthroline) were synthesized and characterized. The single-crystal X-ray diffraction demonstrates that 1–3 are isomorphous, which present dimeric structures with four 4-Cl-2-MOBA anions function as bridging ligands. Complexes 1 and 4–6 display their characteristic luminescence emission bands of central Ln3?ions. The heat capacities, the thermodynamic functions and the thermogravimetry–Fourier transform infrared spectra of gaseous products of complexes 1–6 were investigated.Their non-isothermal kinetics of the second decomposition stage was studied by the integral isoconversional non-linear method and Stark method. Furthermore, 1–6 exhibited excellent antibacterial activity against Candida albicans,Escherichia coli and Staphylococcus aureu.     

Modulation of active Cr(III) complexes by bath preparation to adjust Cr(III) electrodeposition

The preparation process of the Cr(III) bath was studied based on a perspective of accelerating the formation of active Cr(III) complexes. The results of ultraviolet-visible absorption spectroscopy (UV-Vis) and electrodeposition showed that active Cr(III) complexes in the bath prepared at room temperature in several days were rare for depositing chromium. The increase of heating temperature, time, and pH value during the bath preparation promoted the formation of active Cr(III) complexes. The chromium deposition rate increased with the concentration of active Cr(III) complexes increasing. Increasing the heating temperature from 60 to 96℃, the chromium deposition rate increased from 0.40 to 0.71 μm/min. When the concentration of active Cr(III) complexes increased, the grain size of Cr coatings increased, and the carbon content of the coating decreased. It is deduced that Cr(H₂O)₄(OH)L2+ (L is an organic ligand, and its valence is omitted) is a primary active Cr(III) complex.     

Synthesis and reaction of 16-electron Cp<Superscript>t</Superscript>Rh halfsandwich complexes containing 1,2-dichalcogenolate carborane ligands

The reactions of [Cp^tRhCi(μ-Ci)]2 (1) (Cp^t=^tBu2C5H3) with Li2E2C2B10H10 (E = S, Se) lead to the green 16-electron dichaicogenolate complexes Cp^tRh(E2C2B10H10) [E = S(2a), Se(2b)]. The 16-electron complexes 2a and 2b can take up two-electron donor ligands such as tert-butyi isonitrile and carbon monoxide to give the 18-electron dichaicogenolate derivatives Cp^t(L)(E2C2B10H10) [L = ^tBuNC, E =S(3a), Se(3b); L = CO, E = S(4a), Se(4b)]. The molecular structures of complexes 2a and 3a were determined by X-ray crystal structure analysis. The molecular structure of 16-electron complex 2a shows the pseudoaromatic system in IrSe2C2 five numbered ring.     

Synthesis and characterization of N-aryloxo-functiona- lized β-ketoiminate rare-earth complexes and their catalytic activity for the polymerization of ε-caprolactone

The synthesis and characterization of dimeric rare-earth amides stabilized by a dianionic N-aryloxo functionalized ,8-ketoiminate ligand are described. Reactions of 4-（2-hydroxy-5-methyl-phenyl） imino-2-pentanone （LH2） with Ln[N（SiMe3）2]3（μ-Cl）Li（THF）3 in a 1：1 molar ratio in THF gave the dimeric rare-earth amido complexes [LLn{N（SiMe3）2}（THF）]2 [Ln = Nd （1）, Sm （2）, Yb （3）, Y （4）]. These complexes were well characterized, and the definitive molecular structures of complexes 3 and 4 were determined. It was found that complexes 1-4 can initiate the ring-opening polymerization of ε-caprolactone, and the ionic radii of the central metals have significant effect on the catalytic activity.     

Ethylene oligomerization by novel iron(Ⅱ) diimine complexes/MAO

Two novel Fe(Ⅱ) diimine complexes have been synthesized. In combination with MAO, they generate active catalytic systems that oligomerize ethylene with both high catalytic activity and high selectivity for α-olefins. The effects of substituents on the aryl ring, reaction temperatures and molar ratios of Al/Fe on catalytic activity and product distribution are studied.     

Synthesis and Characterization of Quaternary Complexes Ln(CH_2ClCOO)_2 (NO_3) (phen)

Many binary lanthanide complexes have been studied. However, few mixed anion complexes with bidentate heterocyclic amines were synthesized. We synthesized mixed anion complexes Ln ( CH2 ClCOO )2 (NO3 ) ( phen) which was determined by elemental analyses . The IR spectra analyses indicate that NO3- , CH2 ClCOO- and phen are coordinated with Ln . The molar conductances of the complexes at 10-3 mol · L-1 were founded to be between 32.4 and 35.8 S·cm2· mol-1 , suggesting the nonelectrolytes in N-Dimethylformamide. And we determined the fluorescent spectra Eu(CH2ClCOO)2(NO3) ( phen ) and ESR spectra of Gd ( CH2 ClCOO )2 ( NO3) ( phen) .     

Carbon Nanotube-hybridized Supramolecular Hydrogel Based on PEG-b-PDMAEMA /α-cyclodextrin

Well-dispersed multi-walled cabon nanotubes(MWCNTs) were successfully incorporated into a supramolecular hydrogel through combining dual roles of poly(ethylene glycol)-block-poly[(2-dimethylamino) ethyl methacrylate](PEG-b-PDMAEMA) copolymer in dispersing MWCNTs and forming inclusion complexes with α-cyclodextrin(α-CD).Rheological behaviors of supramolecular hydrogels were investigated.The resultant hybrid hydrogels were found to be shear thinning and could be applied as a promising injectable drug delivery system.The mechanical strength of the hybrid hydrogels was greatly improved in comparison with that of the corresponding native hydrogels.     

Synthesis, structure of iron(Ⅲ)-containing imidazolium salts and their catalytic activity in the alkylation of aryl Grignard reagents

A series of iron(III)-containing imidazolium salts of the general formula [DRim][FeX 4 ] (R=2,6-diisopropylphenyl, IPr, X=Cl, 1; R=IPr, X=Br, 2; R=tertbutyl, t Bu, X=Cl, 3; R=isopropyl, i Pr, X=Cl, 4; R=benzyl, Bn, X=Cl, 5; R=Bn, X=Br, 6) have been prepared in high yields via reactions of anhydrous ferric halides with equivalent of the corresponding N,N-dihydro- carby-limidazolium halides, where 2-6 are novel ones. All of the complexes were characterized by elemental analysis, Raman spectroscopy, electrospray ionization mass spectroscopy, and X-ray crystallography for 1 and 2. All of them were non-hygroscopic and air-stable, with four of them existing as solids (1-4) and two as liquids (5 and 6) at room temperature. A preliminary catalytic study on the coupling of 4-tolylmagnesium bromide with cyclohexyl bromide revealed that 1 and 3 possessed the highest activity. In comparison, 2, 4 and 5 exhibited moderate activity and the least active complex was 6.     

Enhancement of transfection efficiency for HeLa cells via incorporating arginine moiety into chitosan

Arginine-rich peptides have attracted considerable attention due to their distinct internalization mechanism. It was reported that arginine and guanidino moieties were able to translocate through cell membranes and played a critical role in the process of membrane permeation. In this work, arginine was conjugated to the backbone of chitosan to form a novel chitosan derivative, arginine modified chitosan (Arg-CS). Arg-CS/DNA complexes were prepared according to the method of coacervation process. The physicochemical properties of Arg-CS and Arg-CS/DNA complexes were characterized and the transfection activity and efficiency mediated by Arg-CS/DNA complexes were investigated taking HeLa cells as target cells. Arg-CS was characterized by FTIR and 13C NMR. Arg-CS/DNA polye- lectrolyte complexes were investigated by agarose gel retardation, dynamic light scattering (DLS) and atomic force microscopy (AFM). The results revealed that the Arg-CS/DNA complexes started to form at N/P ratio of 2:1, and the size of particles varied from 100 to 180 nm. The cytotoxicity of Arg-CS and their complexes with plasmid DNA were determined by MTT assay for HeLa cells, and the results suggested that Arg-CS/DNA complexes were slightly less toxic than Arg-CS. Moreover, the derivative alone and their complexes showed significantly lower toxicity than PEI and PEI/DNA complexes, respectively. Taking HeLa cells as target cells and using pGL3-control as reporter gene, the luciferase expression mediated by Arg-CS was greatly enhanced to about 100 folds compared with the luciferase expression mediated by chitosan at different pH media. These results suggest that Arg-CS is a promising candi- date as a safe and efficient vector for gene delivery and transfection.     

Molecular recognition study on a supramolecular system (ⅩⅤ)──Molecular recognition of aliphatic alcohols by some phenyl-selenium modified β-cyclodextrins

The spectrophotometric titrations have been performed at 298.15 K in buffered aqueous solution (pH 7.20) to give the stability constants (logK-s) for the supramolecular system formed by mono-[6-(phenylseleno)-6-deoxy]-β-cyclodextrin (2), mono-[6-(p-tolylseleno)-6-deoxy]-β-cyclodextrin (3), mono-[6-(o-tolylseleno)-6-deoxy]-β-cyclodextrin (4), mono-[6-(m-tolylseleno)-6-deoxy]-β-cyclodextrin (5) with a series of aliphatic alcohols. The results were compared with the data reported for the parent β-cyclodextrin. The molecular binding ability and selectivity for aliphatic alcohols of modified β-cyclodextrins (2_5) were discussed from the viewpoints of the induced-fit and geometrical complement. The results obtained indicate that the phenylseleno moiety of β-cyclodextrin derivatives (2_5) as a probe for spectrometry can enhance not only the molecular binding ability but also the molecular recognition ability.     

Molecular complex 9,10-anthraquinone-(NO x ) y

9,10-Anthraquinone forms a series of molecular complexes with NO and NO 2,which are stable in solid state or in organic solutions at room temperature and will decompose to original anthraquinone and NO/NO 2 upon heating.The molecular complexes are formed via charge transfer,which is confirmed by a high-resolution mass spectroscopy.By means of reduction,the complexes can be converted to anthrahydroquinone.The mechanism of formation is investigated herein.     

Alternative Models of Iron and Cobalt Catalysts for Ethylene Oligomerization and Polymerization

1 Results Great progresses have been made in the field of transition metal-based complexes as catalytic precursors for olefin oligomerization and polymerization,in which the core subjects will remain as "know and how" to develop novel catalysts both in academic and industrial consideration.The key advantage of iron and cobalt catalyst for ethylene polymerization is to produce vinyl-type polyethylenes.Therefore following the pioneering works of bis(imino) pyridyl iron and cobalt catalyst by Brookhart[1] and Gibson[2] in 1998,there have been many contributions toward their derivatives' complexes for the investigation of their catalytic behaviors.However,there are few examples successful good activity catalysts based upon new designed ligands such as monoiminopyridines[3],2-imino-1,10-phenanthrolines[4],2-benzimidazolylpyridines[5],2-quinoxalinyl-6-imino pyridines[6] and bimetallic complex[7].Those catalysts performed good to high catalytic activities towards ethylene oligomerization and polymerization,meanwhile most of them were first contributed with our efforts inspired by bis(imino)pyridyl metal catalyst.Herein we will present our results with designing pathways,and academic and industrial considerations.     

Synthesis and characterization of carbon-bridged bis(phenolate) lanthanum alkoxides and their catalytic behavior for the polymerization of L-lactide

Four lanthanum alkoxides stabilized by a carbon-bridged bis(phenolate) ligand were synthesized and their catalytic behavior for the ring-opening polymerization of L-lactide was explored. Reactions of [(MBMP)LaCp(THF) 2 ] (MBMP 2 = 2,2′-methylene-bis(6-tert-butyl-4-methyl phenoxo)) with HOCH 2 Ph, HOCH 2 CF 3 , HOCH(CH 3 ) 2 , and HOCH 2 CH 2 N(CH 3 ) 2 , respectively, in a 1:1 molar ratio in THF gave the dimeric lanthanum alkoxo complexes [(MBMP)Ln(μ-OR)(THF) 2 ] 2 (OR = OCH 2 Ph(1), OCH 2 CF 3 (2), OCH(CH 3 ) 2 (3), OCH 2 CH 2 N(CH 3 ) 2 (4)]. These complexes were well characterized, and the definitive molecular structure of complex 1 was determined. It was found that complexes 1 to 4 are efficient initiators for the ring-opening polymerization of L-lactide. The structure of the alkoxo groups has a significant effect on the catalytic behavior, and complex 2 can initiate L-lactide polymerization in a controlled manner.     

Synthesis and Characterization of Quaternary Complexes [Ln(CH_2=C(CH_3)-COO)_2(NO_3)(phen)]_2

Many trinary lanthanide complexes have been studied. However, few mixed anion complexes with bidentate heterocyclic amines were synthesized. Mixed anion complexes [Ln (CH2=C(CH3)-COO)2(NO3)(phen)]2 was synthesized and its properties were determined by elemental analyses, IR and TGA. The IR spectra analysis indicate that NO3- , CH2=C(CH3)-COO- and Phen are coordinated with Ln. And the fluorescent spectra of [Eu(CH2=C(CH3)-COO)2(NO3)(phen)]2 and 1H NMR spectra of [La(CH2=C(CH3)-COO)2 (NO3)(phen)]2 was determined respectively.