氮杂环卡宾双核金络合物催化的胺芳基化反应

联萘胺出发合成了氮杂环卡宾双核和单核金络合物, 通过X射线的单晶衍射确定了它们的结构, 并将其应用于催化胺芳基化反应中, 以高达95%的收率得到吡咯烷类化合物. 综合上述实验结果, 发现氮杂环卡宾双核金络合物4b中存在着Au(I)-Au(I)间相互弱作用力, 而且这种弱相互作用可能对该催化反应起重要的作用, 以高收率得到吡咯烷类化合物.     

双核Au(I)磷硫配合物激发态性质和金属间弱相互作用的从头算研究

采用MP2和CIS方法分别优化双核Au(I)磷硫配合物, [Au₂(SHCH₂SH)₂]^2＋ (1), [Au₂(SHCH₂SH)(PH₂CH₂PH₂)]^2＋(2), [Au₂(PH₂CH₂PH₂)₂]^2＋ (3), [Au₂(SHCH₂SH)(SCH₂S)] (4), [Au₂(PH₂CH₂PH₂)(SCH₂S)] (5)和[Au₂(SCH₂S)₂]^2－ (6), 基态和激发态的结构. 计算结果表明基态时1～6中存在Au(I)-Au(I)弱吸引作用, 激发态时1～5的金属间相互作用明显增强而6则减弱, 这与实验研究结果一致. 单激发组态相互作用计算揭示: 磷硫配体的更替使得Au(I)配合物跃迁性质呈现MC→MMLCT→MLCT的规律性变化(MC: 金属中心; MMLCT: 金属金属到配体电荷转移; MLCT: 金属到配体电荷转移).     

A novel mononuclear gold(I) complex: Synthesis and x-ray structure of [Au{P(C6H5)3}3][SiF5] · 1.5 CH2Cl2

Tris(triphenylphosphine)gold(I)-pentafluorosilicate(IV) ([Au{P(C₆H₅)₃}₃][SiF₅]) was prepared and the structure was determined by single crystal x-ray diffraction. The complex crystallizes in the triclinic space group P1 (No. 2). The lattice constants are a = 14.634(2) Å, b = 17.180(2) Å, c = 22.212(3) Å, α = 86.48(1)°, β = 78.95(1)°, γ = 83.99(1)°. Number of molecules per cell: Z = 4. The gold atoms are coordinated to three triphenylphosphine ligands to form the trigonal planar cation [Au{P(C₆H₅)₃}₃]⁺. Separated from the cation is the [SiF₅]^? anion which is regular trigonal bipyramidal coordinated. No interactions between the fluorine atoms and the gold atoms were observed.     

Antiproliferative Activity of Gold(I) N-Heterocyclic Carbene and Triphenylphosphine Complexes with Ibuprofen Derivatives as Effective Enzyme Inhibitors

A series of gold(I) complexes of ligand ibuprofen-alkynyl (but-3-yn-1-yl 2-(4-isobutylphenyl)propanoate, LE) with N-heterocyclic carbene (LC: 1,3-dimethylimidazol-2-ylidene) and triphenylphosphine (PPh₃) ligands with formula (LE)Au (LC) (complex 1 ) and (LE)Au (PPh₃) (complex 2 ) were synthesized and fully characterized by spectroscopic methods. In order to reveal the cytotoxicity mechanism, the interaction of complex 1 or 2 with cysteine (HCys) has been studied by experimental and density functional theory (DFT) methods. The compounds were investigated for their anticancer activity against MCF-7, MDAMB 231 breast cancer cells, HT-29 colon cancer cells and MCF-10A non-tumor breast cell line. The results were compared with cisplatin and auranofin as reference drugs. The complex 2 showed more cytotoxic activity than complex 1 . The complex 2 was 4.2, 3.7, and 1.7 fold more active than cisplatin against HT-29, MDA-MB-231, MCF-7 cancer cell lines, respectively. The inhibition of thioredoxin reductase of complexes 1 and 2 including cytosolic (TrxR1) and mitochondrial (TrxR2) thioredoxin reductase and also the inhibition of glutathione reductase (GR) were studied in detail. Moreover, the cellular uptake and reactive oxygen species (ROS) generation of compounds were investigated. Based on the DFT calculations a relationship between the σ-donor ability of the isolated ligands and cytotoxicity is suggested.     

Synthesis and Supramolecular Structure of Chloro（1,10-phenanthroline ）copper（I） Hexahydrate

1INTRODUCTION Atom transfer radical addition is an efficient me-thod for carbon-carbon bond formation in organic synthesis[1,2].In some of these reactions,a transi-tion-metal catalyst acts as a carrier of the halogen atom in a reversible redox process.The transition-metal-catalyzed has been successfully used to con-trol radical polymerization[3].In the process,the transition-metal species initially abstracts halogen atom X from organic halide to form oxidized species and carbon-centered r…     

Using Room Temperature Phosphorescence of Gold(I) Complexes for PAHs Sensing

The synthesis of two new phosphane-gold(I)–napthalimide complexes has been performed and characterized. The compounds present luminescent properties with denoted room temperature phosphorescence (RTP) induced by the proximity of the gold(I) heavy atom that favors intersystem crossing and triplet state population. The emissive properties of the compounds together with the planarity of their chromophore were used to investigate their potential as hosts in the molecular recognition of different polycyclic aromatic hydrocarbons (PAHs). Naphthalene, anthracene, phenanthrene, and pyrene were chosen to evaluate how the size and electronic properties can affect the host:guest interactions. Stronger affinity has been detected through emission titrations for the PAHs with extended aromaticity (anthracene and pyrene) and the results have been supported by DFT calculation studies.     

碘·(N,N'联吡啶)·(三苯基膦)合铜(I)的合成和晶体结构

铜（Ｉ）配合物的研究在金属酶的化学模拟和配合物结构及反应性能等研究方面具有重要的理论和实际意义［１］。但由于铜（Ｉ）配合物不稳定,且在多数有机溶剂中的溶解度较小,铜（Ｉ）配合物的合成比较困难。我们在铜（Ｉ）配合物的合成方面积累了一些经验,合成了一系列含有三苯基膦和氮杂环配体的铜（Ｉ）配合物［ＣｕＸ（ＰＰｈ３）Ｌ］ｎ［２～４］（ｎ＝１,Ｘ＝Ｉ,Ｌ＝１,１０ｐｈｅｎ;ｎ＝２,Ｘ＝Ｂｒ,Ｉ,Ｌ＝Ｃ９Ｈ７Ｎ）,并对它们的结构进行了研究。本文报道一个类似的新配合物［ＣｕＩ（ＰＰｈ３）（ｂｐｙ）］（Ｉ）的合成…     

具有银-银相互作用的二(3-吡啶基)嘧啶-银(Ⅰ)配合物及其荧光性质

用分层法合成了两个配合物[Ag2(L)2](CF3COO)2(1)和[Ag2(L)2](CF3SO3)2(2)[L=2-甲基-4,6-二(3-吡啶基)嘧啶],并用元素分析、红外光谱、X-射线单晶衍射等手段对其进行了表征。晶体结构分析结果表明:具有双核大环结构的配合物1和2由Ag(Ⅰ)…Ag(Ⅰ)相互作用连接形成一维链状结构,并进一步通过π-π相互作用形成二维层状结构。研究了配合物2的荧光性质。     

冠醚环化二硫烯双核Au(I)配合物的合成、结构及电化学性质

合成了含有冠醚环化二硫烯的双核Au(I)配合物[(30-C2S4)Au2(PPh3):](1),[(40-C2S4)Au2·(PPh3)2](2),[(30一C6-S8)Au2(Pph3)2](3)和[(40-C6-S8)Au2(PPh3)2](4)以及富硫配合物[(btdt)Au2·(PPh3)2](5).通过x射线...     

Selective Formation of Intramolecular Hydrogen-Bonding Palladium(II) Complexes with Nucleosides Using Unsymmetrical Tridentate Ligands

Three palladium(II) complexes with amino-amidato-phenolato-type tridentate ligands were synthesized and characterized by ¹H NMR spectroscopy and X-ray crystallography. The strategic arrangement of a hydrogen-bond donor and acceptor adjacent to the substitution site of the Pd^II complex allowed the selective coordination of nucleosides. Among two pyrimidine-nucleosides, cytidine and 5-methyluridine, cytidine was successfully coordinated to the Pd^II complex while 5-methyluridne was not. On the other hand, both purine-nucleosides, adenosine and guanosine, were coordinated to the Pd^II complex. As purines have several coordination sites, adenosine afforded three kinds of coordination isomers expected from the three different donors. However, guanosine afforded a sole product according to the ligand design such that the formation of double intramolecular hydrogen-bond strongly induced the specific coordination by N1-position of guanine moiety. Furthermore, the preference of the nucleosides was evaluated by scrambling reactions. It was found that the preference of guanosine is nearly twice as high as adenosine and cytidine, owing to the three-point interaction of a coordination bond and two hydrogen bonds. These results show that the combination of a coordination and hydrogen bonds, which is reminiscent of the Watson–Crick base pairing, is an effective tool for the precise recognition of nucleosides.     

二个含水杨酰腙配体的钒配合物的合成与晶体结构研究

2种水杨酰腙配体H2L1(H2L1=邻羟基苯乙酮缩水杨酰腙)和H2L2(H2L2=水杨醛缩水杨酰腙)分别与VO(acac)2反应,合成了2个钒配合物[VOL1(C2H5O)]2(1)和[VOL2(i-C3H7O)](2),利用元素分析、红外光谱、紫外光谱和单晶衍射等手段进行表征。配合物1是由酚氧原子桥联2个金属中心形成的具有晶体学中心对称性的双核钒(V)配合物结构,每个V(V)原子具有扭曲的八面体配位构型。配合物2为单核结构,每个V(V)原子具有扭曲的四角锥配位构型,相邻的配合物分子通过分子间氢键作用形成一维超分子链状结构。采用循环伏安法研究了化合物2的电化学性质。     

Synthesis and Crystal Structure of a New Silver(I) Complex

The reaction of 4-amino-6-methyl-1,2,4-triazine-3(2 H)-thione-5-one (AMTTO) with silver(I) nitrate in methanol gives the complex [Ag(AMTTO)₂]NO₃ ( 1 ). 1 was characterized by IR and ¹³C NMR spectroscopy and by an X-ray structure analysis [space group C2/c, Z = 4, lattice dimensions at –80 °C: a = 1306.7(2), b = 1139.0(2), c = 1089.2(1) pm, β = 94.54(1)°, R₁ = 0.0294]. The cation possesses a highly distorted linear coordination sphere in the solid state.     

Synthesis and Liquid Crystal Behaviors of 2,4-Dioxo-3-pentyl 4-decyloxy Cinnamate Rhodium （I） Complexes

The title complexes have been synthesized by the reaction of [RhCI(CO)2]2 or [RhCI(COD)]2 (COD = 1,5-cyclooctadiene)with the organic ligand 2,4-dioxo-3-pentyl 4-decyloxy cinnamate 2. The complex 3 based on dicarbonylrhodium(I) shows nematic phase, while the complex 4 containing rhodium(I) bound to a COD ligand is a nonmesogen. The relationship between molecular structures and liquid crystal behavior has also been discussed by means of computer-aided molecular modeling.     

Supramolecular gold(I) compounds with trithiocyanuric acid: Self‐assembly and luminescent properties

[(N₃S₃)Au(AuPMe₃)₂]₂ ( 1 ) and [(N₃S₃)Au(AuPEt₃)₂]₂ ( 2 ) were prepared by treating AuCl(PMe₃) or AuCl(PEt₃) with H₃N₃S₃ upon deprotonation by trimethylamine to give respective Au₆ supermolecules. Using dppm(AuCl)₂ instead of AuCl(PMe₃) or AuCl(PEt₃) to react with H₃N₃S₃ in a similar reaction condition led to a rare heptanuclear supermolecule of [(N₃S₃)₂Au₇(dppm)₄]Cl ( 3 ). It is noted that besides short intramolecular gold(I)?gold(I) distances, both compounds 1 and 2 also show intermolecular gold(I)?gold(I) distances of 3.067(1) and 3.241(1) Å, resulting in two‐dimensional and one‐dimensional polymeric gold(I) solid, respectively. In fact, compound 1 shows a similar two‐dimensional polymeric gold(I) solid to that of the reported [(N₃S₃)Au(AuPPhMe₂)₂]₂ with an intermolecular gold(I)?gold(I) distance of 3.130(2) Å. Significantly, these intermolecular gold(I)?gold(I) distances are well correlated with their cone angles and emission energies. For example, intermolecular gold(I)?gold(I) distances increase in the order of 3.067(1) Å < 3.130(2) Å < 3.241(1) Å for PMe₃ (118°), PPhMe₂ (122°), and PEt₃ (132°), and their emission energies also increase in the order of 542 nm < 530 nm < 504 nm, respectively. This work highlights a very good correlation between intermolecular aurophilic interactions and emission energies for a series of Au₆ supermolecules, where the cone angle plays a vital role in the self‐assembly process as well. Finally, the emissions for 1 – 3 are tentatively assigned to the S → Au charge‐transfer transition, whereas they are most probably modified by gold(I)?gold(I) interactions.     

Two- and Three-dimensional Frameworks with (6,3) and (10,3)-a Topology from Self-assembly of Three-connecting Organic Ligands with Cadmium(II) and Silver(I) Salts

Assembly of three-connecting ligands 1,3,5-tris(1-imidazolyl)benzene (tib) and 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titmb) with cadmium(II) and silver(I) salts provide new metal-organic frameworks, [Cd(tib)₂](NO₃)₂·4H₂O (1), [Ag(tib)(PPh₃)](CF₃SO₃) (2) and [Ag(titmb)(PPh₃)](CF₃SO₃)·1.5H₂O (3) (PPh₃=triphenylphosphine). Single-crystal X-ray diffraction studies reveal that complexes 1 and 3 are two-dimensional honeycomb networks, while complex 2 is a noninterpenetrated three-dimensional architecture with (10,3)-a topology. The results indicate that the nature (structure and flexibility) of the organic ligands and the bulky auxiliary ligand have great impact on the assembly and structure of metal-organic frameworks. The photoluminescent properties of the synthesized complexes were studied in the solid state at room temperature.     

Synthesis and Physico-Chemical Properties of Homoleptic Copper(I) Complexes with Asymmetric Ligands as a DSSC Dye

To develop low-cost and efficient dye-sensitized solar cells (DSSCs), we designed and prepared three homoleptic Cu(I) complexes with asymmetric ligands, M1, M2, and Y3, which have the advantages of heteroleptic-type complexes and compensate for their synthetic challenges. The three copper(I) complexes were characterized by elemental analysis, UV-vis absorption spectroscopy, and electrochemical measurements. Their absorption spectra and orbital energies were evaluated and are discussed in the context of TD-DFT calculations. The complexes have high V_OC values (0.48, 0.60, and 0.66 V for M1, M2, and Y3, respectively) which are similar to previously reported copper(I) dyes with symmetric ligands, although their energy conversion efficiencies are relatively low (0.17, 0.64, and 2.66%, respectively).     

Novel Copper(I) Complexes and Clusters with Phosphorus-Sulfur and Sulfur-Sulfur Containing Ligands

Abstract

The synthesis and coordination chemistry of ligands bearing PS donor groups in complexes with copper(I) halides, in particular thiophosphites, thiophosphonites, and thiophosphinites, are described.     

Antimicrobial and Anticancer Application of Silver(I) Dipeptide Complexes

Three silver(I) dipeptide complexes [Ag(GlyGly)]_n(NO₃)_n (AgGlyGly), [Ag₂(GlyAla)(NO₃)₂]_n (AgGlyAla) and [Ag₂(HGlyAsp)(NO₃)]_n (AgGlyAsp) were prepared, investigated and characterized by vibrational spectroscopy (mid-IR), elemental and thermogravimetric analysis and mass spectrometry. For AgGlyGly, X-ray crystallography was also performed. Their stability in biological testing media was verified by time-dependent NMR measurements. Their in vitro antimicrobial activity was evaluated against selected pathogenic microorganisms. Moreover, the influence of silver(I) dipeptide complexes on microbial film formation was described. Further, the cytotoxicity of the complexes against selected cancer cells (BLM, MDA-MB-231, HeLa, HCT116, MCF-7 and Jurkat) and fibroblasts (BJ-5ta) using a colorimetric MTS assay was tested, and the selectivity index (SI) was identified. The mechanism of action of Ag(I) dipeptide complexes was elucidated and discussed by the study in terms of their binding affinity toward the CT DNA, the ability to cleave the DNA and the ability to influence numbers of cells within each cell cycle phase. The new silver(I) dipeptide complexes are able to bind into DNA by noncovalent interaction, and the topoisomerase I inhibition study showed that the studied complexes inhibit its activity at a concentration of 15 μM.     

(Phosphine)gold(I) Complexes of Benzenedithioles. Crystal structures of 1,2-benzenedithiolato-bis[triphenyl-phosphinegold(I)] and bis(triethylphosphine)gold(I) bis(1,2-benzenedithiolato)gold(III)

The reaction of 1,2- and 1,3-benzenedithiol C₆H₄(SH)₂ with chloro(phosphine)gold(I) complexes R₃PAuCl (R = Et, Ph) in the presence of triethylamine in tetrahydrofuran gives stable gold(I) complexes 1,2-C₆H₄(SAuPR₃)₂ [R = Et ( 1 ) and Ph ( 2 )] or 1,3-C₆H₄(SAuPPh₃)₂ ( 3 ), respectively, in high yield. The compounds have been characterized by analytical and NMR spectroscopic data. From the reaction of 1,2-C₆H(SH)₂ with Et₃P? AuCl a by-product [(Et₃P)₂Au]⁺ [Au(1,2? C₆H₄S₂)₂]^? ( 4 ) has also been isolated in low yield. The crystal structures of compounds 2 and 4 have been determined by single crystal X-ray diffraction. The gold(I) atoms in complex 2 are two-coordinate with bond angles S? Au? P of 175.2(1) and 159.5(1)°, Au? S bond distances of 2.304(1) and 2.321(1) å, and a short Au…?Au contact of 3.145(1) Å. The gold(I) atom in the cation of complex 4 is also linearly two-coordinate with a P? Au? P angle of 170.1(1) Å and Au? P distances of 2.296(3) and 2.298(3) Å. The geometry of the anion in 4 shows a square-planar coordination of gold(III) by two chelating 1,2-benzenedithiolate ligands with Au? S distances between 2.299(3) and 2.312(3) Å (for two crystallographically independent, centrosymmetrical anions in the unit cell).