TERNARY Cu(Ⅱ)(ATP)AND HETEROAROMATIC N BASE COMPLEXES IN SOLUTION:STABILITY CONSTANTS AND ANTITUMOR MECHANISM EXPLORATION

The stability of the complexes of four pyridine-like ligandswith Cu(ATP)~(2-) was studied and by comparing the stability constants of theternary complexes[Cu(ATP)L]~(2-) with those of the binary complexes[CuL]~(2+),astacking interaction between the pyridine ring and the purine ring of ATP isindicated.It is possible to interpret the antitumor mechanism of[Pt(NH_3)_8(N-het)Cl]Cl in terms of this stacking interaction.     

Synthesis and Crystal Structure of cis—[meso—1,3—Bis（propylsulfinyl）propane]dichloroplatinum（Ⅱ）

1 INTRODUCTION A number of Pt complexes with monosulfoxide have been isolated and characterized[1]. It was indicated that the sulfoxide group trends to coordinate to soft metals (Pt, Pd, etc.) by its sulfur atom[2]. Pt(Ⅱ) trends to bond to disulfoxides in cis-mode and such complexes have potential antitumor activity[2]. However, only few examples of such complexes have been structurally characterized[3]. We will report herein the crystal structure of a new Pt(Ⅱ) complex with a disulf…     

DFT and TDDFT investigations on the ground and excited states for polynuclear platinum(II) complexes containing the rigid phenylacetylide ligand

We have studied the ground and excited states of the three dendritic polynuclear Pt(II) complexes 1-[Cl(PH3)2PtC≡≡ C]-3,5-[HC≡≡ C]C6H3 (1), 1,3-[Cl(PH3)2PtC≡≡ C]2-5-[HC≡≡ C]C6H3 (2), and 1,3,5-[Cl(PH3)2- PtC≡≡ C]3C6H3 (3), by using the B3LYP and UB3LYP methods, respectively. TDDFT approach with the PCM model was performed to predict the emission spectra properties of 1―3 in CH2Cl2 solution. We first predicted the excited-state geometries for the three complexes. With the change of the number of Pt(II) atom, 1―3 show the different geometry structures in both the ground and excited states; fur- thermore, the increase of the metal density from 1 to 3 results in the red shift of the lowest-energy emissions along the series. The luminescent properties of 1 are somewhat different from those of 2 and 3. The emission properties of 2 and 3 are richer than 1. Our conclusion can give a good support for designing the high efficient luminescent materials.     

Syntheses, Characterizations, Crystal Structures and Antibacterial Activities of Two Zinc(II) Complexes with a Schiff Base Derived from o-Vanillin and p-Toluidine

Two new zinc(II) complexes, [Zn2L2Cl4]·2[ZnL(CH3OH)Cl2] 1 and [ZnL2(NO3)2] 2, were synthesized by reacting ZnX2·nH2O (X = Cl-, NO3-) and a Schiff base ligand 2-[(4-me- thylphenylimino)methyl]-6-methoxyphenol (C15H15NO2, L) which was obtained by the condensation of o-vanillin (2-hydroxy-3-methoxybenzaldehyde) with p-toluidine. Both 1 and 2 were characterized by single-crystal X-ray diffraction technique, elemental analysis, molar conductance, FT-IR, UV-Vis, 1H-NMR spectra and thermogravimetric analysis. The Schiff base ligand and its zinc(II) complexes have been tested in vitro to evaluate their antibacterial activity against bacteria, viz., Escherichia Coli, Staphylococcus aureus and Bacillus Subtilis. The results show that these complexes have higher activity than the corresponding free Schiff base ligand against the same bacteria.     

STYRENE POLYMERIZATION BY OGANOLATHANIDE COMPLEXS[(Bu~tCp)_2LnCH_3]_2 (Ln=Pr,Nd,Gd)

Complexes(Bu~tCp)_1LmC1 react with LiCH_3 in molar ratio of 1:1 to give theneutral methyl complexes[Bu~tCp)_2LnCH_3]_2 (Ln=Pr,Nd,Gd).The complexes alone showmodest catalytic activity for the polymerization of styrene.The polymerizationactivity depends markedly on lanthanide elements.The activity order is Na Pr Gd and the polymerization mechanism was proposed.     

A Novel Platinum（Ⅳ） Halide Anion as Ethyl-triphenylphosphenonium Salt： Synthetic, Structural and Theoretical Study

1 INTRODUCTION The importance of metal ions in nucleic acid and other biologic processes has stimulated considerable research interest in the area of metal interactions with nuclei acid constituents[1, 2] due to the discovery that some platinum compounds, especially cis-Pt (NH3)2- Cl2, exhibit carcinostatic properties[3]. This has led to an increased research activity in the chemistry and structures of platinum complexes containing novel or- ganic ligands. And crystal engineering has its…     

新型取代硅桥联茂稀土化合物的合成及在纳米级氢化钠助催化剂作用下高活性催化甲基丙烯酸甲酯聚合的研究

The synthesis and characterization of four new silicon-linked lanthanocene complexes with pendant phenyl groups on cyclopentadiene were reported. Based on the data of elemental analyses, MS and IR, the complexes were presumed to be unsolvated and dimeric complexes [Me2Si(C5H3CMe2C6H5)2LnC1]2 [Ln=Er (1), Gd (2), Sm (3), Dy (4)]. In conjunction with AlEt3 or sodium hydride as the co-catalyst, these complexes could efficiently catalyze the polymerization of methyl methacrylate (MMA). When the nanometric sodium hydride was used as a co-catalyst, the complexes were highly effective for the polymerization of MMA. At low temperature and in short time, in [MeESi(C5H3CMe2C6H5)2LnC1]2/NaH (nanometric) system, the polymer was obtained in more than 80% yield and the molecular weight was greater than 105. The activity reached that of organolanthanide hydride as a single-component catalyst. In ]MeESi(C5H3CMe2C6H5)2ErC1]2/Nail (nanometric) system, the effects of the molar ratio of MMA/catalyst and catalyst/co-catalyst, and the temperature on polymerization were studied.     

Nickel Complexes Bearing Bidentate Schiff Base as Ethylene Oligomerization Catalysts

Several nickel complexes [N,N]NiBr2, in which IN,N] indicates bidentate nitrogen-containing ligands (1: [N,N]=N-(2,6-diisopropylphenyl)pyridine-2-carboxaldimine (Cl8H22N2); 2: N-(2,6-diisopropylphenyl)-6-methylpyridine-2-carboxaldimine (C19H24N2); 3: N-(2,4,6-trimethylphenyl)pyridine-2-carboxaldimine(Cl5Hl6N2); 4: N-(2,4,6-trimethylphenyl)-6-methylpyridine-2-carboxaldlmlne (Cl6Hl8N2) were synthesized. Some of the nickel complexes exhibit high activity for ethylene oligomerization in the presence of an organoaluminum activator. The main factor affecting the activity and the structure of oligomers is the steric effect of substituents on [N,N] ligands. Methylaluminoxane (MAO) -activated catalysts showed higher activities and produced oligomers with higher molecular weight than Et2AlCl-activated ones. The oligomerization in toluene rather than hexane results in much higher activity, and the oligomers produced in toluene have relatively high molecular weight. With activation of MAO or Et2AlCl,the [N,N]NiBr2 system tended to produce highly branched oligomers with low α-olefin content, but the α-olefin content could be increased by changing the reaction conditions.     

[Cu(2,2'-bpy)Cl2]和[Cu(1,10-phen)C12]在多金属氧酸盐上的多相化:选择性氧化四氢化萘的新催化剂

Mononuclear Cu(II)bipyridine(1)and phenantroline complexes(2)were synthesized and immobilized by different procedures on H3PW12O40 polyoxometalate(POM).Characterization by XRD and SEM-EDX were performed to assess the preservation of the Keggin structure and stoichiometry of the complex.The immobilized complexes were tested as heterogeneous catalysts for the partial oxidation of tetralin(1,2,3,4-tetrahydronaphthalene)using hydrogen peroxide as oxidant in acetonitrile/water as solvent.[Cu(2,2’-bpy)Cl][H2PW12O40] and[Cu(1,10-phen)Cl][H2PW12O40]oxidized tetralin at room temperature,with 16%conversion with(2),to 1-tetralone and 2-tetralone with 83%selectivity.However,the selectivity for 1-tetralone was only 56%.Different preparation methods for the heterogenization of these complexes on the POM Keggin unit were compared and used to enhance the selectivity to 1-tetralone to 75%.     

Molecular design and theoretical investigation into one-and two-photon absorption properties of two series of cyclometalated platinum(Ⅱ) complexes

We have theoretically investigated two series of cyclometalated Pt(Ⅱ) complexes,a series [Pt(C,N,N) Cl] and b series [Pt(C,N,Npyrazolyl) Cl].The geometrical and electronic structures are calculated at the ECP60MWB//6-31G*(H,C,Cl,N,S) basis set level using DFT method;one-photon absorption(OPA) properties are calculated by using both TDDFT and ZINDO methods and two-photon absorption(TPA) properties are obtained with the ZINDO/SOS method.The resonance integrals parameters(βsp and βd) for Pt are adjusted to -1 and -28.5 eV,respectively,to make max OPA wavelength calculated by ZINDO closest to the experimental data and TDDFT results.The calculated results indicate the molecule 2b([Pt(Cnaphthyl,N,Npyrazolyl) Cl]) has the biggest potential as outstanding TPA materials because(i) the TPA properties of b series are more outstanding in IR wavelength range,the molecules in b series have good transparencies and possess 1-pyrazolyl-NH that is also available for another metal coordination(e.g.,dimerization) and chemical interactions;(ii) when C is Cnaphthyl in the C,N,N ligand of cyclometalated Pt(Ⅱ) complexes,the molecules have the best conjugation effect and the best TPA properties.     

SYTHESE AND REACTIONS OF HETEROBINUCLEAR COMPLEXES [PhCl_2SnM(Cl)(CO)_3(CH_3CN)_2] (M = Mo, W)

Abstract The complexes [M(CO)_3(CH_3CN)_3](M=Mo, W)react with an equimolar quantity ofPhSnCl_3 in dichloromethane at room tempreture to afford new heterobinuclearcomplexes [PhCl_2SnM(Cl)(CO)_3(CH_3CN)_2] [M=Mo(1); W(2)]. The complexes reactwith two equivalents of PR_2R'(R=Ph, R'=Ph, Me; R=Cy, R'=H) to yield stablecomplexes [PhCl_2SnM(Cl)(CO)_3(PR_2R')_2]. Reaction of[PhCl_2SnM(Cl)(CO)_3(CH_3CN)_2]with one equivalent of PPh_2(CH_2)nPPh_2(n=I,2) or bulky phosphine ligands PBu_2~tClin dichloromethane at room tempreture to give [PhCl_2SnMo(Cl)(CO)_3{PPh_2(CH_2)n-PPh_2}] .CH_2Cl_2, [PhCl_2SnMo(Cl)(CO)_3PBu_2~tCl]. CH_2Cl_2, respectively. The complexes1 and 2 react with phosphite donor ligands P(OMe)_3 to give [PhCl_2SnM(Cl)(CO)_2-{P(OMe)_3}_3]. All complexes have been characterized by elemental analysis, IRand ~1HNMR spectroscopies. Here we report the preliminary results of this work.     

Syntheses, Characterizations, Crystal Structures and Antibacterial Activities of Two Zinc（II） Complexes with a Schiff Base Derived from o-Vanillin and p-Toluidine

Two new zinc（Ⅱ） complexes, [Zn2L2Ch].2[ZnL（CH3OH）Cl2] 1 and [ZnL2（NO3）2] 2, were synthesized by reacting ZnX2.nH2O （X = Cl^-, NO3^-） and a Schiff base ligand 2-[（4-methylphenylimino）methyl]-6-methoxyphenol （C15HIsNO2, L） which was obtained by the condensation of o-vanillin （2-hydroxy-3-methoxybenzaldehyde） with p-toluidine. Both 1 and 2 were characterized by single-crystal X-ray diffraction technique, elemental analysis, molar conductance, FT-IR, UV-Vis, IH-NMR spectra and thermogravimetrie analysis. The Schiff base ligand and its zinc（Ⅱ） complexes have been tested in vitro to evaluate their antibacterial activity against bacteria, viz., Escherichia Coli, Staphylococcus aureus and Bacillus Subtilis. The results show that these complexes have higher activity than the corresponding free Schiff base ligand against the same bacteria.     

Synthesis,spectral studies,thermal behavior,and antibacterial activity of Ni(Ⅱ),Cu(Ⅱ),and Zn(Ⅱ) complexes with an ONO tridentate Schiff base

Three new transition metal complexes have been synthesized with a Schiff base,3-(2-hydroxy-5-chlorophenylimino)-l,3- diphenylpropen-1-one.In all complexes Schiff base is completely deprotonated and coordinated to metal as tridentate ligand via phenolic and enolic oxygens and imine nitrogen.Thermal decomposition of the complexes has been studied by thermogravimetry. The in vitro antibacterial activity of Schiff bases and their complexes has been evaluated and compared with the standard drugs.     

Synthesis,Crystal Structure and Electrochemistry of Two Complexes （YLn）3＋[PW12O40]3-（L=Me2SO,Me2NCHO）

The reaction of α-H3[PW12O40] with Y（NO3）3 in the presence of DMF or DMSO leads to two complexes with the formulae {Y（DMSO）7}·PW12O40（1） and {[Y（DMF）7]2PW12O40}·PW12O40（2）. The crystal structures indicate that complex 1 consists of discrete [YLn]3＋ cations and α-Keggin heteropolyanions [PW12O40]3-, whereas, in complex 2, donor-acceptor interaction results in a cation-anion-cation triplet. In addition, the electrochemical behavior of the two complexes indicates the usual successive reduction processes of the W atoms in the anions.     

SYNTHESES OF POLYMER-BOUND RHODIUM COMPLEXES AND THEIR APPLICATION AS CATALYSTS FOR THE HYDROFORMYLATION OF DIISOBUTYLENE (Ⅰ)

Copolymer of styrene-divinylbenzene in bead form (with DVB 8%, average pore radius 3.0×10~2, specific surface area 25m~2/g, particle size 0.2—0.4mm) was made by the suspension polymerization. After chloromethylation, the beads were then reacted with lithium diphenyl phosphine and various amines separately. Two types of polymeric ligands, i.e. polyvinylbenzyl diphenyl phosphine and eight kinds of polyvinylbenzyl amines were thus obtained. In order to prepare the polymer-bound rhodium complexes, the ligands were then reacted with [Rh(CO)_2CI]_2. The initial composition and structure of the polymeric complexes were verified by IR spectra. The complexes synthesized above were used to catalyze the hydroformylation of diisobutylene under conditions of 110℃, 100(120) kg/cm~2 and H_2/CO=1:1. The effects of the donor atoms (N, P) on the activity of the two types of catalysts and the N-substituted groups on the activity 'of polymeric amine-rhodium complexes were examined.     

STUDIES ON STRUCTURES OF SOME PLATINUM COMPLEXES WITH 1, 1-CYCLOPROPANEDICAR BOXYLATE

The crystal structure, of [Pt(NH_3)_2CPrDCA]. H_2O (Ⅰ), [Pt(CH_3NH_2)_2CPrDCA] (Ⅱ), and [Pt(dmbn) CPrDCA]·2.5H_2O(Ⅲ) (where CPrDCA is 1, 1-cyclopropanedicarboxylate; dmbn is 2, 3-dimethyl-2, 3-butyldiamine) are determined. Compound Ⅰ crystallizes in the orthorhombic space group P_(nma) with the cell dimensions: a=6.517(2), b=9.709(3), c=14.205(5), Z=4, R=0.058. Compound Ⅱ is monoclinic with space group P2_1/n, a=9.648(3), b=8.720(2), c=12.770(4), β=107.12(2), Z=4, R=0.059. Compound Ⅲ belongs to the monoclinic system space group P2_1/m with the cell dimensions: a=6.494(1), b=19.638(3), c=6.606(1), β=94.44(1), Z=2, R=0.038.Electronic structures of the complexes are studied and the correlstion between structure of the amine ligands and biological activity of the complexes is explored.     

Interaction of Mixed Porphyrin-polypyridyl Ru(II) Complex with Bovine Serum Albumin

The interactions of mixed porphyrin-polypyridyl Ru(II) complexes [m(Py-3′)TPP-Ru(phen) 2 Cl] + (1) and its derivatives [Nim(Py-3′)TPP-Ru(phen) 2 Cl] + (2) and [Cum(Py-3′)TPP-Ru(phen) 2 Cl] + (3)(phen=1,10-phenanthroline; m(Py-3′)TPP=5-(3′-pyridyl)-10,15,20-triphenylporphyrin) with bovine serum albumin(BSA) were investigated by fluorescence, UV-Vis and circular dichroism(CD) spectroscopies. The UV-Vis and CD spectral experiments indicated that the secondary structures of the protein were perturbed in the presence of the porphyrin Ru(II) complex and the perturbation was enhanced under the irradiation with ultra-violet light. The fluorescence quenching mechanism of BSA by the three complexes was determined to be a static process, and the apparent binding constant K values for complexes 1, 2 and 3 measured by fluorescence quenching method were (3.86±0.03)×10 3 L/mol(n=0.94±0.04), (5.69±0.04)×10 3 L/mol(n=1.03±0.06), and (6.54±0.02)×10 3 L/mol(n=1.03±0.05), respectively.     

Synthesis,Structure and Slow Magnetization Relaxation of Co(Ⅱ) Complexes from a Flexible Imidazole-based Ligand

The employment of a flexible imidazole-based ligand(H_2L), condensed from 1 Himidazole-2-carbaldehyde and 1,2-bis(aminooxy)ethane, and Co~(2+) salt has led to the formation of Co(Ⅱ) complexes [Co(H_2L)_2Cl]Cl·4CH_3OH(1) and [Co(H_2L)(NCS)_2]_2·2C_4H_(10)O(2), in the presence of different anions, i.e, Cl-and SCN-, respectively. Single-crystal X-ray analyses show that complex 1 with a square pyramid(C_(4v)) local environment exhibits a two-dimensional(2D)layered(4,4)-net framework and complex 2 displays a dinuclear molecule box with a T_d local environment. By comparison between complexes 1 and 2, the versatile configuration of ligand including cis-and trans-form isomer has a significant effect on the structures of the resulting complexes. The magnetic properties of 1 and 2 are also investigated. The ac magnetic susceptibility revealed that 2 exhibits the characteristic of slow magnetization relaxation.     

Two Ion-pair Complexes Constructed by[M（mnt）2]n- （M=Ni,Co,mnt = Maleonitriledithiolate）:Syntheses,Characterization and Thermal Stability

Two new ion-pair complexes [Co(BBP)2]2[Ni(mnt)2]Cl2·4DMF·2H2O(1, BBP =2,6-bis(benzimidazol-2'-yl) pyridine, mnt = maleonitriledithiolate) and [(Py)2CH2][Co(mnt)2]2·4DMF(2) have been synthesized and characterized by elemental analyses, IR spectroscopy,thermogravimetric analyses and single-crystal X-ray diffraction. X-ray diffraction studies show that complex 1 crystallizes in monoclinic, space group P21/c. The crystal of 2 belongs to a triclinic system with space group P1. Due to the hydrogen bonding interactions, anions and cations formed the mixed packing in complex 1 while the anions and cations formed segregated columns in 2. In addition, thermogravimetric analyses of the two complexes are also investigated.     

A MODEL STUDY ON MODE OF BONDING OF CISPLATIN WITH DNA

The interaction of cis-[Pt(NK_3)_2Cl_2] with nucleosides, as constituents of DNA, was studled by spectrophotometric, ~(13)C NMR and CNDO/2 methods. The apparent stability constants of the complexes formed and the initial rate of formation were determined. The sites of binding of nucleoside (or nucleotide) with Cisplatin were ascertained and the electronic structure of the model coordination compounds of Cisplatin and guanine was calculated by MO approach. On the basis of the obtained results, the mechanism of the antitumour action of Cisplatin was discussed, and a new possible mode of bonding of Cisplatin with DNA was proposed.