SYNTHESIS AND POLYMERIZATION OF 2-OXO-3-METHYLENE-5, 6-DIPHENYL-1,4-DIOXAN

A new cyclic monomer, 2-oxo-3-methylene-5, 6-diphenyl-1, 4-dioxan, was synthesized. Thestructure of the intermediates and the monomer were determined by IR,~1H NMR,~(13)C NMR andelemental analysis. This new monomer is different from other cyclic monomers in this series,it isa solid (mp 108--109℃)and not very reactive, but still can undergo free radical ring-openingpolymerization. The free radical polymerization was carried out at 130℃. The structure of theresulting polymer was discussed and charaterized by IR, ~1H NMR, ~(13)C NMR and elementalanalysis. The molecular weight of the polymer was estimated by viscosity determination.     

SYNTHESIS AND ANIONIC POLYMERIZATION OF 2-METHYL-2-METHOXY CARBONYL-5-METHYLENE-1, 3-DIOXOLAN-4-ONE

A new cyclic monomer, 2-methyl-2-methocycarbonyl-5-methylene 1,3-dioxlan-4-one,wassynthesized successfully. The monomer and intermediate were characterized by ~1H NMR,~(13)C NMR, INEPT (Intensive Nuclei Enhanced by Polarization Transfer) technique, IR andelemental analysis. Anionic polymerization of the monomer was carried out in anhydrous THF at.70℃, and 9-fluorenyllithium was used as initiator. The polymer strucure was determined byIR, NMR and elemental analysis. Molecular weight of the polymer was estimated by viscositymeasurement in DMSO at 30℃.     

Synthesis and characterization of tris(η~5-cyclopentadienyl-μ-carbonyliron)-μ_3-nitrosyl cluster:X-ray structure of[(η~5-C_5H_5)(μ-CO)Fe]_3(μ3-NO).C_4H_8O

Tris)(η 5-cyclopentadienyl-μ-carbonyl-iron)-μ3-nitrosyl cluster was obtained from the reaction of cyclopentadienyl dicarbonyliron dimer with nitrogen monoxide in xylene. The cluster was characterized by elemental analyses, IR, MS and 1H NMR. The crystal structure of [(η5-C5H5)(μ-CO)Fe]3(μ3-NO).C4H8O was determined by X-ray diffraction analysis. It crystallizes in the orthorhombic space group Pnma, a=9.053(2), 6=10.545(2), c=22.525(4) A, V=2150.3(7) A3, Z=4,Dc=1.68 g.cm-3; structure solution and refinement based on 1141 reflections with I > 3.0 (I) (MoKa, A=0.71073 A) converged at R=0.0540. The infrared absorption band at 1325 cm-1 of the μ3-NO in the cluster, which is red shifted, shows that μ3-NO is activated.     

SYTHESIS AND ANIONIC POLYMERIZATION OF 2-METHYL-2-METHOXYCARBONYL-5-METHYLENE-1, 3-DIOXOLAN-4-ONE

A new cyclic monomer, 2-methyl-2-methoxycarbonyl-5-methylene-1,3-dioxolan-4-one,was synthesized successfully. The monomer and intermediate were characterized by ~1H NMR, ~(13)CNMR, INEPT(Intensive Nuclei Enhanced by Polarization Transfer) technique, IR and elementalanalysis. Anionic polymerization of the monomer was carried out in anhydrous THF at -70℃,and 9-fluorenyllithium was used as initiator. The polymer structure was determined by IR, NMRand elemental analysis. Molecular weight of the polymer was estimated by viscosity measurementin DMSO at 30℃.     

Synthesis and characterization of MH···HOR dihydrogen bonded ruthenium and osmium complexes(η~5-C_5H_4CH_2OH)MH(PPh_3)_2(M = Ru,Os)

Treatment of RuCl2(PPh3)3 with 6-dimethylaminopentafulvene in THF in the presence of water produced(η5-C5H4CHO) RuCl(PPh3)2, which was reduced by NaBH4 to give the Ru–H···HO dihydrogen bonded complex(η5-C5H4CH2OH) RuH(PPh3)2. The dihydrogen bonded complex(η5-C5H4CH2OH)RuH(PPh3)2 could also be synthesized by the reduction of complex(η5-C5H4CHO)RuH(PPh3)2, which was obtained by the reaction of RuHCl(PPh3)3 with 6-dimethylaminopentafulvene in the presence of water. The analogous dihydrogen bonded osmium complex(η5-C5H4CH2OH)OsH(PPh3)2 was similarly prepared. Single crystal structures and DFT calculations support the presence of intra-molecular H···H interaction, with separations of around 1.9 to 2.0 .     

Synthesis,reactivity and electrochemical properties of substituted cyclopentadienyl cobalt (Ⅲ) complexes

Cyclopentadienyl cobalt complexes (n5-C5H4R)CoLI2 [L = CO,R=-COOCH2CH=CH2 (3); L=PPh3,R=-COOCH2-CH=CH2 (6); L= P(p-C6H4CH3)3,R=-COOC(CH3) = CH2 (7),-COOCH2C6H5(8),-COOCH2CH = CH2 (9)] were prepared and characterized by elemental analyses,1H NMR,IR and UV-vis spectra.The reaction of complexes (n5-C5H4R)CoLI2[L=CO,R=-COOC(CH3)=CH2 (1) ,-COOCH2C6H5(2):L=PPh3,R =-COOC(CH3)=CH2 (4),-COOCH2C6H5(5)] with Na-Hg resulted in the formation of their corresponding substituted cobaltocene (n5-C5H4R)2Co [R= -COOC(CH3) = CH2 (10),-COOCH2C6H5 (11) ].The electrochemical properties of these complexes 1-11 were studied by cyclic voltammetry.It was found that as the ligand (L) of the cobalt (Ⅲ) complexes changing from CO to PPh3 and P(p-tolyl)3,their oxidation potentials increased gradually.The cyclic voltammetry of α,α'-substituted cobaltocene showed reversible oxidation of one electron pro-     

Synthesis, Electrochemistry, and Photophysics of a Novel Binuclear Polypyridyl Ru(Ⅱ) Complex with an 1,8-Adipoylamidobis(1,10-phenanthroline-5-yl) Ligand

The present paper covers the syntheses of 1,8-adipoylamido-bis(1,10-phenanthroline-5-yl)(bphaa) and its binuclear complex {[(bpy)2Ru]2(bphaa)}(PF6)4, where bpy is 2,2′-bipyridine. The two novel compounds were confirmed by means of elemental analysis, IR, LD-MS and 1H NMR, and 1H NMR spectra were completely assigned in virtue of 1H-1H COSY. The electrochemical behavior of the binuclear Ru(Ⅱ) complex was obtained using cyclic and square-wave voltammetry. Its photophysical property was investigated by electronic absorption, fluorescence excitation and emission spectra.     

Preparation, Structure and Electrochemical Property of a Pyrazole-substituted Diiron Dithiolate Complex

A pyrazole-substituted diiron dithiolate complex [Fe2(μ-pdt)(CO)5(3,5-Me2Pz)](1,3,5-Me 2Pz=3,5-dimethylpyrazole) was prepared as a biomimetic model for the active site of [FeFe]-hydrogenase by CO-substitution of all-carbonyl complex [Fe2(μ-pdt)(CO)6] with 3,5-Me2Pz. The molecular structure was confirmed by MS, IR, 1H NMR, elemental analysis and single-crystal X-ray analysis. Complex 1 crystallizes in the triclinic system, space group P1 with a=9.108(7), b=9.743(8), c=11.192(9), α=109.235(5), β=101.914(9), γ=96.605(6)o. In CH3CN solution, reversible transformation between 1 and the acetonitrile-substituted species [Fe2(μ-pdt)-(CO)5(NCCH3)] was detected by both IR and cyclic voltammetry (CV). The electrochemical proton reduction catalyzed by 1 in the presence of acetic acid was also studied in CH2Cl2.     

Study on the inclusion compound of β-cyclodextrin with (η5-cyclopentadienyl)tricarbonylmanganese(0)

The supramolecular inclusion compound of β-cyclodextrin (β-CD, host) with (η5-cyclopentadienyl)tricarbonylmanganese [MnCp(CO)3, guest] was obtained in a crystalline state. The host-guest compound is thermally stable and do not liberate the guest on heating at 100$ in vacuum. It was characteried by elemental analysis,1H NMR, differential scanning thermal (DSC) analysis and TLC. Continueous variation plot by NMR method shows that β-CD formed 1:1 inclusion compound with MnCp(CO)3. On the basis of 1H NMR spectra and the model building with Corey Pauling Koltum (CPK) models, the most probable inclusion mode is proposed.     

One-pot synthesis and characterization of a new, branched polycarbosilane bearing allyl groups

A highly branched polycarbosilane bearing allyl groups has been prepared by a one-pot synthesis with chloromethyltrichlor-osilane, chloromethylmethyldichlorosilane and allyl chloride as the starting materials. The resultant polymer, with the approximate formula [SiH1.2(CH3)0.71(CH2CH=CH2)0.09CH2]n, has been characterized by 1H, 13C, and 29Si NMR, GPC, TG and elemental analysis. It could be cross-linked thermally at 170℃in the absence of oxygen. Pyrolysis of the polymer gave a ceramic with a yield of about 70%.     

STUDY ON POLYMERIZATION MECHANISM OF 3, 9,-DIALLYL-3, 9, -DIBENZYL-1, 5, 7, 11-TETRAOXASPIRO [5, 5] UNDECANE

A new monomer, 3,9-diallyl-3, 9-dibenzyl-1, 5,7,11 - tetraoxa- spiro [5,5] undecane (6) was prepared by the reaction of 2- allyl- 2' - benzyl- propanediol - 1.3 with dibutyltin oxide, and then treated with CS_2. Monomer 4 could be initiated by cationic initiators to give a viscous polymer (white powder in the case of polymerization at 0℃). Upon the NMR and IR spectra of the obtained polymer, the components and their relative amount were estimated. The polymerization mechanism was discussed.     

丙酮酸异烟酰腙四核有机锡配合物的合成、表征及{[nBu2Sn(C9H8N3O3)O]SnBu3n}2的晶体结构

The tetranuclear alkyltin(Ⅳ) compounds {[R2Sn(C9H8N3O3)O]SnR3}2 [R=n-Bu (1), 4-CNC6H4CH2 (2),C6H5CH2 (3), 4-ClC6H4CH2 (4)] were prepared by the reaction of Schiff base ligand pyruvic acid isonicotinyl hydrazone with (R3Sn)2O in the corresponding molar ratio of 1:1. All compounds have been characterized by elemental analysis, IR and ^1H NMR spectra. The crystal structure of compound 1 was determined by X-ray single crystal diffractional analysis. This compound exhibits a dimeric structure containing distannoxane units with two types of the tin atoms. For the first tin atom, it appears to be seven-coordinated with a distorted pentagonal bipyramid geometry, and the other is five-coordinated with a distorted trigonal bipyramidal geometry. The molecules are packed in the unit cell in two-dimensional network structure through an interaction between the N atoms of the pyridine and the tin atoms of an adjacent molecule.     

Synthesis, Structure and Luminescent Properties of a New Terbium（Ⅲ） Complex with 5-Bromoisophthalic Acid

The self-assembly of 5-bromoisophthalic acid (H2BIPA) with Tb(NO3)3·6H2O under hydrothermal conditions gives rise to a 3D coordination polymer, [Tb2(BIPA)3(CH3CH2OH)]n (1), which was characterized by elemental analysis, IR and single-crystal X-ray diffraction. The crystal is of monoclinic system, space group P21/c with a = 19.2591(17), b = 8.2537(7), c = 18.5663(17), β = 104.4720(10)°, V = 2857.6(4)3, C26H15Br3O13Tb2, Mr = 1092.95, Dc = 2.540 g/cm3, F(000) = 2040, μ = 9.173 mm-1 and Z = 4. The final R = 0.0324 and wR = 0.0767 for 5299 observed reflections (I > 2σ(I)). Complex 1 displays an unusual three-dimensional (4,6)-connected network with (48.66.8)2(44.62)2(42.84) topology, which is different from [Tb(HBDC)(BDC)(H2O)4]·3.3H2O (BDC = isophthalate) because the -Br substituent of isophthalate results in different electronic effect and steric hindrance to change the coordination modes of carboxylate groups in the assembly process. Moreover, luminescent properties of 1 have also been investigated in the solid state.     

SYNTHESIS AND FREE RADICAL POLYMERIZATION OF 2-OXO-3-METHYLEN E-5-PHENYL-1,4-DIOXAN

The novel cyclic monomer, 2-oxo-3-methylene-5-phenyl-1,4-dioxan, was synthesized by a set of reactions. Several intermediates were prepared and characterized in order to determine the monomer structure. The presence of chiral centers in the intermediates and resulting monomer makes it complicated to separate , purify and characterize them. It is a very reactive monomer which will polymerize even at room temperature if expose to moisture and air. This monomer can undergo essentially quantitative flee radical ring opening polymerization. The driving force for ring opening is the formation of new carbonyl group and benzylic radical. The monomer and polymer structure were established by IR, ~1H NMR, ~(13)C NMR and elemental analysis or high resolution mass spectrum. The molecular weight of the resulting polymer was estimated by viscosity determination.     

Synthesis,Structure and Spectral Properties of a Novel Triaryl Substituted Triazole and Its Co(Ⅱ) Complex

The new compound 3-(2-pyridyl)-4-(p-methoxyphenyl)-5-(2-thienyl)-1,2,4-triazole L was synthesized and characterized by elemental analysis,IR,1H NMR,13C NMR,MS,UV and photoluminescent spectra.The complex CoL2(NCS)2 was prepared by the reaction of ligand L with Co(SCN)2,and its structure was characterized by single-crystal X-ray diffraction,IR,UV,elemental analysis and MS.The complex crystallizes in monoclinic,space group P21/n with a=13.7639(19),b=7.6641(11),c=18.409(3),β=101.549(3)o,V = 1902.6(5) 3,Z=2,C38H28CoN10O2S4,Mr=843.87,Dc=1.473 g/cm3,μ=0.720 mm-1,S=1.075,F(000)=866.0,the final R=0.0825 and wR=0.2149 for 2566 observed reflections(I2σ(I)).In the crystal structure,the cobalt atom adopts a distorted octahedral environment with two NCS-ions in the axial positions and two bidentate chelating L ligands in the equatorial plane.The extended 2D network of the complex is formed by intermolecular C-H…N hydrogen bonds together with π-π stacking interactions.     

SYNTHESIS AND POLYMERIZATION OF BISPHENYLENE ORTHOCARBONATE

Bisphenylene orthocarbonate (Ⅱ) was synthesized by the reaction of dicopper catecholate with carbon tetrachloride, and underwent cationic ring-opening polymerization with the introduction of phenyl group into the main chain. The obtained polymer with ester and ether group was verified by IR and ~1H NMR spectra. Based on the analysis of the polymer structures, the polymerization mechanism was proposed. Its T_m and T_(?) are 254℃and 160℃respectively. No decomposition of the polymer was observed below 320℃. The volume expansion property of the monomer during polymerization was studied by measuring the density difference between Ⅰand its polymer at various temperatures.     

Synthesis, Crystal Structure and Properties of Complex VO（C10H9NO3） （C13H10NO2）

Complex VO(C10H9NO3)(C13H10NO2)(C10H9NO2-3=N-salicylidene-L-alaninate, C13H10NO-2=N-phenylbenzohydroxamate) was synthesized and characterized by means of elemental analysis, IR, UV, 1H NMR spectroscopies, cyclic voltammetry and single crystal X-ray diffraction. The complex crystallized in a monoclinic system with space group P21 and crystal cell parameters a=0.9720(1) nm, b=1.8274(2) nm, c=1.2542(1) nm, β=104.868(9)°, V=2.1532(4) nm3, Mr=470.34, Z=2. The two oxygen atoms and the one nitrogen atom of the tridentate Schiff base ligand and the one oxime oxygen atom of the hydroxamate ligand coordinate to the vanadium atom, forming an equatorial plane, the two axial positions are respectively occupied by the oxygen atom of the oxovanadium and the carbonyl oxygen atom of the hydroxamate and the vanadium atom exhibits a distorted octahedral VO(ONO)(OO) coordination sphere. The 1H NMR spectrum suggests that the two isomers, endo and exo in a molar ratio of 1/1.7, coexist in the solution of the title complex in CDCl3. There exists a quasi-reversible one-electron redox reaction corresponding to VⅤ/VⅥ couple in the three non-aqueous solvents, and the redox potential E1/2 of the title complex substantially shifts in the direction of the positive voltage increase in the order: CH2Cl2＜CH3CN＜DMF.     

Synthesis,Crystal Structure,and Thermal Stability of a Dibutyltin Complex {[4-Et2NC6H3（O）C=NC6H3（O）- 5-NO2]（n-Bu2Sn）}2 and Its Interaction with DNA

The Schiff base organotin(IV) complex {[4-Et2NC6H3(O)C=NC6H3(O)-5-NO2](nBu2Sn)}2 has been synthesized via the reaction between 4-(diethylamino) salicylaldehyde-2-amino-4-nitrophenol Schiff base(H2L) and dibutyltin oxide. Complex C1 has been characterized by IR, 1H NMR, 13 C NMR spectra, and elemental analysis, and its crystal structure was determined by X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 15.6559(8), b = 9.1657(5), c = 18.8351(10) , β = 107.3440(10)°, Z = 4, V = 2579.9(2) 3, Dc = 1.442 Mg·m-3, μ(MoKα) = 1.025 mm-1, F(000) = 1152, R = 0.0250 and wR = 0.0633. The central Sn atom is coordinated in a hexadentate manner to assume a distorted octahedral configuration. Complex C1 was studied by TGA analysis in air atmosphere. The interaction between complex C1 and the herring sperm DNA was realized through the intercalation of the complex based on the studies by EB fluorescent probe.     

A Novel Three-dimensional Triazole-based Zinc(Ⅱ) Coordination Polymer Controlled by the Spacers of Dicarboxylate Ligand with(4~2,6~2,8~2)(4,6~2,8~3) Topology

A novel mixed-ligand coordination polymer [Zn(BTA)(ip)0.5]n(1, HBTA = benzotriazole, H2 ip = isophthalic acid) has been synthesized under hydrothermal conditions, which was further characterized by X-ray diffraction, IR spectrum, elemental analysis and TG-DTA experiments. Complex 1 crystallizes in monoclinic system, space group Pnma with a = 8.9731(5), b = 22.0477(12), c = 10.0217(5) ?, V = 1982.66(18) ?3, Z = 8, C10 H6 ZnN3 O2, Mr = 265.55, Dc = 1.779 g/cm3, μ = 2.462 mm-1, F(000) = 1064, the final R = 0.0225 and wR = 0.0652 with I 2?(I). This complex is a 3 D framework with the(42,62,82)(4,62,83) topology. Furthermore, the thermal stability of complex 1 is observed to be dependent on the polymeric structure nature. Strong solid-state luminescence emissions suggest that complex 1 is a good candidate for light emission materials.     

Synthesis,Characterization and Molecular Structure of a Diiron Complex(μ-SCH_2CH_2CH_2S-μ)Fe_2(CO)_5(Ph_2PCH_3)

The title complex,(μ-pdt)Fe_2(CO)_5(Ph_2PCH_3)(pdt = SCH_2CH_2CH_2S),was obtained by the reaction of the parent complex(μ-pdt)Fe_2(CO)_6 with Ph_2PCH_3 and Me_3NO·2H_2O in good yield(90%). The title complex was characterized by IR,~1H NMR,~(31)P{~1H} NMR and ~(13)C{~1H} NMR spectroscopy as well as by single-crystal X-ray diffraction analysis. The molecular structure shows that the title complex contains a butterfly diiron propanedithiolate cluster with five terminal carbonyls and a monophosphine ligand Ph_2PCH_3. The crystal packing diagram reveals that intermolecular C H···O hydrogen bonds between CH_2 and carbonyls,π-π stacking interactions and van der Waals' interactions stabilize the solid state to form a three-dimensional network.