Ru-Fe异金属化合物及其在Au表面上SAM的电化学研究

为使不对称Ru-Fe化合物能在表面上自组装形成单分子膜,对trans-RuCl(dppm)₂(C≡CFc)[Fc=C₅H₄FeC₅H₅,dppm=(C₆H₅)₂PCH₂P(C₆H₅)₂](1)进行修饰,得到Ru(dppm)₂(C≡CFc)(C≡CPhOCH₃)(2),[Ru(dppm)₂(C≡CFc)(N≡CCH₂CH₂NH₂)][PF₆](3)和[Ru(dppm)₂(C≡CFc)(N≡CCH₂CH₂NHC(O)·(CH₂)₁₀SH)][PF₆](4),并详细研究了该系列化合物的电化学性质.循环伏安结果显示出Ru周围配体得失电子能力的差别,直接影响了Ru中心的氧化-还原性,但这种影响并没有通过共轭的炔键传递到二茂铁中的Fe中心.化合物4可以在Au表面上自组装形成稳定、有序的单分子膜.还利用循环伏安法研究了单分子膜的形成过程及其表面覆盖率.     

Heterobimetallic Gold/Ruthenium Complexes Synthesized via Post-functionalization and Applied in Dual Photoredox Gold Catalysis

The synthesis of heterobimetallic Au^I/Ru^II complexes of the general formula syn- and anti-[{AuCl}( L1 ∩ L2 ){Ru(bpy)₂}][PF₆]₂ is reported. The ditopic bridging ligand L1 ∩ L2 refers to a P,N hybrid ligand composed of phosphine and bipyridine substructures, which was obtained via a post-functionalization strategy based on Diels-Alder reaction between a phosphole and a maleimide moiety. It was found that the stereochemistry at the phosphorus atom of the resulting 7-phosphanorbornene backbone can be controlled by executing the metal coordination and the cycloaddition reaction in a different order. All precursors, as well as the mono- and multimetallic complexes, were isolated and fully characterized by various spectroscopic methods such as NMR, IR, and UV-vis spectroscopy as well as cyclic voltammetry. Photophysical measurements show efficient phosphorescence for the investigated monometallic complex anti-[( L1 ∩ L2 ){Ru(bpy)₂}][PF₆]₂ and the bimetallic analogue syn-[{AuCl}( L1 ∩ L2 ){Ru(bpy)₂}][PF₆]₂, thus indicating a small influence of the {AuCl} fragment on the photoluminescence properties. The heterobimetallic Au^I/Ru^II complexes syn- and anti-[{AuCl}( L1 ∩ L2 ){Ru(bpy)₂}][PF₆]₂ are both active catalysts in the P-arylation of aryldiazonium salts promoted by visible light with H-phosphonate affording arylphosphonates in yields of up to 91 %. Both dinuclear complexes outperform their monometallic counterparts.     

钛钼异双核配合物的合成及结构研究

合成了13个钛-钼异双核金属有机配合物,测定了它们的碳、氢、氮、钛及钼的含量,还测定了~1H、~(13)C、~(11)B及~(95)Mo NMR和红外、质谱、电导数据.确认该类配合物分子中存在Ti-Mo之间的金属-金属键和一个桥羰基键,并具有如下结构:其中R=H,Pz(吡唑基);R'=CH_3,OCH_3,OC_2H_5;X=H,CH_3;Y=H,CH_3.     

Diastereoselective Synthesis, Spectroscopy, and Electrochemistry of Ruthenium(II) Complexes of Substituted Pyrazolylpyridine Ligands

We report the synthesis of the hetero- and homoleptic ruthenium(II) complexes Ru(bpy)(2)L(2+), Ru(bpy)L(2)(2+) (bpy is 2,2'-bipyridine), and RuL(3)(2+) of six new bidentates L, the substituted pyrazolylpyridines 1-6 (1-substituted-3-(2-pyridinyl)-4,5,6,7-tetrahydroindazoles with substituents R = H, CH(3), Ph, or C(6)H(4)-4"-COOX where X = H, CH(3), or C(2)H(5)). These were fully characterized by (1)H- and (13)C-NMR spectroscopy and elemental analysis. The UV-visible spectra and redox properties of the complexes, some in the ruthenium(III) and reduced bipyridine oxidation states, are also discussed. The substituents R played a role in determining the stereochemistry of the Ru(bpy)L(2)(2+) and RuL(3)(2+) products. The reaction of Ru(DMSO)(4)Cl(2) with 3 equiv of L bearing aromatic substituents gave only meridional RuL(3)(2+) isomers. The one-step reaction of Ru(bpy)Cl(3).H(2)O with 2 equiv of L provided a mixture of the three possible Ru(bpy)L(2)(2+) isomers, from which one symmetric isomer (labeled beta) was isolated pure. A trans arrangement of the pyrazole groups was deduced by (1)H-NMR and confirmed by X-ray crystallography for one such stereomer (beta-[Ru(bpy)(5)(2)](PF(6))(2), R = C(6)H(4)-4"-COOC(2)H(5)). In contrast, Ru(DMSO)(4)Cl(2) reacted with 2 equiv of L and then 1 equiv of bpy to selectively form the other symmetric isomer (labeled alpha) where the pyridine groups of L are trans. Crystal data for beta-[Ru(bpy)(5)(2)](PF(6))(2) (C(52)H(50)N(8)O(4)F(12)P(2)Ru) with Mo Kalpha (lambda = 0.710 73 ?) radiation at 295 K: a = 28.442(13) ?, b = 18.469(15) ?, c = 23.785(9) ?, beta = 116.76(0) degrees, monoclinic, space group C2/c, Z = 8. Fully anisotropic (except for H and disordered F atoms), full-matrix, weighted least-squares refinement on F(2) gave a weighted R on F(2) of 0.2573 corresponding to R on F of 0.1031 for data where F > 4sigma(F ).     

Chromium,Molybdenum and Ruthenium Complexes of 2-Hydroxyacetophenone Schiff Bases

Interaction of the Schiff base 2-hydroxyacetophenonepropylimine (happramH) with M(CO)₆, M=Cr or Mo under reduced pressure gave the dicarbonyl complex M(CO)₂(happramH)₂. The complex MoO(happram)₂ was isolated from the reaction of Mo(CO)₆ and happramH in air. Ru₃(CO)₁₂ and RuCl₃ reacted with the Schiff base bis-(2-hydroxyacetophenone)ethylenediimine (hapenH₂) to give Ru(CO)₂(hapenH₂) and [RuCl₂(hapenH2)]Cl. Elemental, spectroscopic and magnetic studies of the reported complexes revealed the proposed structures. The thermal properties of the complexes were investigated by thermogravimetric techniques. Cyclic voltammetry of the complexes showed tautomeric redox processes due to ligand-based reduction and metal-based oxidation.     

Synthesis and Study of Ruthenium Phthalocyanine Complexes

Methods of synthesis of ruthenium tetra-tert-butylphthalocyaninate (Pc ^t Ru) were developed. The synthesis performed in both autoclave and in open system (in isoamyl alcohol in the presence (1,8-diazabicyclo[5,4,0]undecene) resulted in Pc ^t Ru() containing CO as axial ligand. When quinoline was used in the synthesis of Pc ^t Ru, the Pc ^t Ru(Iqnl)₂ complex was obtained with two isoquinoline molecules (Iqnl) as axial ligands, which were detached consecutively in the course of thermogravimetric analysis. The compounds formed were studied by different physicochemical methods: electron, IR, and ¹H NMR spectroscopies, MALDI-TOF mass spectroscopy, thermogravimetric and elemental analyses.     

Synthesis and Characterization of Some Ruthenium Mixed-Ligand Complexes

The complexation reaction of trans-[RuCl₂(Dpte)₂] (Dpte – (diphenylthio)ethane) with mixed diimine ligands 2,2"-bipyridine, pyridylquinoline, 4,6-dichloro-2-(2-pyridyl)pyrimidine, 4,6-dichloro-5-methyl-2-(2-pyridyl)pyrimidine, and 4,6-dichloro-5-phenyl-2-(2-pyridyl)pyrimidine produces new Ru(II) mixed-ligand complexes. These complexes exhibit maximum photo- and chemical stability and high absorptivity. The above complexes have been characterized using IR, ¹H and ¹³C NMR, electronic absorption spectroscopy, and elemental analysis.     

钌多吡啶配合物的合成及结合DNA的研究

合成了咪唑并［ｆ］邻菲咯啉（ＩＰ）和２－苯基咪唑并［ｆ］邻菲咯啉（ＰＩＰ）两种新的配体及［Ｒｕ·（ｂｐ）２（ＩＰ）］￣（２＋）（简称ｂ２ＩＰ）、［Ｒｕ（ｂｐｙ）２（ＰＩＰ）］￣（２＋）（简称ｂ２ＰＩＰ）、［Ｒｕ（ｐｈｅｎ）２（ＩＰ）］￣（２＋）（简称ｐ２ＩＰ）和［Ｒｕ（ｐｈｅｎ）２（ＰＩＰ）］￣（２＋）（简称ｐ２ＰＩＰ）４种新混配物。用电子吸收、稳态发光、圆二色谱研究了配合物与小牛胸腺ＤＮＡ的结合情况。总的结合强度顺序为：ｂ２ＩＰ＜ｂ２ＰＩＰ≤ｐ２ＩＰ＜ｐ２ＰＩＰ，这与配体的平面大小、π电子扩展程度和疏水性顺序（ｂｐｙ＜＜ｐｈｅｎ＜ＩＰ＜ＰＩＰ）是一致的。证明了配合物与ＤＮＡ存在插入结合。ＣＤ谱表明这种结合有对映体选择性．     

Bioorthogonal Catalytic Activation of Platinum and Ruthenium Anticancer Complexes by FAD and Flavoproteins

Recent advances in bioorthogonal catalysis promise to deliver new chemical tools for performing chemoselective transformations in complex biological environments. Herein, we report how FAD (flavin adenine dinucleotide), FMN (flavin mononucleotide), and four flavoproteins act as unconventional photocatalysts capable of converting Pt^IV and Ru^II complexes into potentially toxic Pt^II or Ru^II?OH₂ species. In the presence of electron donors and low doses of visible light, the flavoproteins mini singlet oxygen generator (miniSOG) and NADH oxidase (NOX) catalytically activate Pt^IV prodrugs with bioorthogonal selectivity. In the presence of NADH, NOX catalyzes Pt^IV activation in the dark as well, indicating for the first time that flavoenzymes may contribute to initiating the activity of Pt^IV chemotherapeutic agents.     

Synthesis and Structure of Platinum Diethyl Sulfoxide Complexes

Russian Journal of General Chemistry - The reaction of tetraorganylphosphonium and tetraethylammonium chlorides with hexachloroplatinic acid hydrate in a mixture of acetonitrile and diethyl...     

Synthesis of Heterobimetallic Phosphido-Bridged W-Mo Complexes with Chelating dppe and dppm Ligands

Reactions between and bidentate phosphines (dppm and dppe) produced complexes and with chelating dppm and dppe ligands as only products. No bridging bidentate phosphine complex was observed. Both complexes were spectroscopically characterized.     

钌卟啉轴向配合物的合成与结构表征

采用一种简单的合成方法, 以钌羰基卟啉(1)和二氧钌卟啉(2)为原料, 与不同的氨基酸酯作用, 得到系列单氨基酸酯羰基和双氨基酸酯为轴向配体的钌卟啉配合物(4a~4c和5a~5d). 所有化合物均经过红外光谱、 核磁共振谱和质谱等表征手段确证为目标化合物, 并用X射线单晶衍射测定了化合物4a的分子结构, 这对研究钌卟啉与生物大分子的相互作用具有重要的意义.     

含金属钌配合物的可溶性三元聚酰亚胺的合成与表征

通过改变与6FDA共缩聚的两种二胺单体的比例,在分子主链中引入具有庞大侧基的9,9-二苯基芴单元,然后和金属钌配合物进行配位,得剑了三个含金属钌配合物的三元聚酰哑胺BFPI-1-Ru,BFPI-2-Ru和BFPI-3-Ru.用元素分析、GPC、FT-IR、TG和UV-Vis等对其分子量、结构及性质进行了表征.结果表明,随9,9-二苯基芴单元含量的增加,含金属聚合物在低沸点溶剂CHCl_3和THF中的溶解性提高.所合成的含金属聚酰亚胺具有良好的热稳定性,在350～800nm较宽的紫外可见光区有良好的光吸收性质.     

新的双胺双膦钌配合物的合成、表征和催化性能

Polydentate ligands, N,N'-bis[o-(diphenylphosphino)benzylidene]-1,2-propane-diamine [P2N2Me for short] and N,N'-bis[o-(diphenylphosphino)benzy1]-1,2-propanediamine [P2N2 H4Me for short] have been synthesized. The interaction of RuCl2(DMSO)4 with one equivalent of P2N2Me or P2N2H4Me in refluxing toluene gave trans-RuCl2(P2N2Me) and trans-RuCl2(P2N4H4Me) in good yield, respectively. The ligands and the complexes have been fully characterized by elemental analysis and spectroscopic methods. The complexes act as an excellent catalyst precursor in hydrogen transfer hydrogenation of acetophenone in catalyst: acetophenone :iso-PrOK of 1: 100: 15, leading to 2-phenylethanol of 89-96% yield.     

Chiral Steroidal Phosphines: Synthesis and Platinum Complexes

 The synthesis of novel 3- and 17-diphenylphosphino-androstane derivatives via homogeneous catalytic P-C coupling is described. The products were characterized by ¹H and ³¹P NMR measurements. According to the NMR investigation of the PtCl₂P₂-type complexes, the steroidal phosphines are trans-coordinated with respect to the Pt-centre exclusively.     

Chiral Steroidal Phosphines: Synthesis and Platinum Complexes

Summary.  The synthesis of novel 3- and 17-diphenylphosphino-androstane derivatives via homogeneous catalytic P-C coupling is described. The products were characterized by ¹H and ³¹P NMR measurements. According to the NMR investigation of the PtCl₂P₂-type complexes, the steroidal phosphines are trans-coordinated with respect to the Pt-centre exclusively. Received June 14, 2000. Accepted (revised) July 24, 2000     

新型功能材料有机钌络合物和有机钌聚合物

有机钌络合物和有机钌聚合物具有特殊的光、电性能,是一种新型功能材料,正在形成一个新的研究领域。本文介绍有机钌络合物和有机钌聚合物的光致电子转移、光致发光和电致发光等现象以及它们在发光二极管、发光电池、氧化传感器等方面的应用。     

pH敏感铱、钌和铂配合物在肿瘤靶向荧光成像和治疗中的应用

肿瘤组织的微酸性环境为肿瘤准确诊断和有效治疗提供了新思路。pH敏感性金属配合物因具有较高的物理化学稳定性,突出的光谱特性和肿瘤靶向性等性质,引起高度关注。本文综述了这种肿瘤酸性微环境的产生机制以及近年来对这种酸性微环境敏感的铱、钌、铂配合物作为肿瘤成像和治疗试剂的研究进展。     

Ruthenium-azoimine-chloranilates Synthesis,Spectra and Electrochemistry of Ruthenium(II)-1-alkyl-2-(arylazo)imidazole-chloranilate Complexes

Ag⁺-assisted dechlorination of blue cis-trans-cis Ru(R-aai-R′)₂Cl₂ followed by the reaction with chloranilic acid (H₂CA) in the presence of Et₃N, gives a neutral mononuclear violet complex [Ru(R-aai-R′)₂(CA)]. [R-aai-R′=p-R-C₆H₄—N=N—C₃H₂—NN, abbreviated as an N,N′ chelator where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), OMe (b), NO₂ (c) and R′= Me (4), Et(5), Bz(6)]. All the complexes exhibit strong intense MLCT transitions in the visible region and weak broad bands at higher wavelength (>700 nm). Visible transitions (580–595 nm) show a negative solvatochromic effect. The cyclic voltammograms show two quasireversible to irreversible couples positive to SCE and are due to CA⁻/CA²⁻ (1.2–1.35 V) and Ru(III)/Ru(II) (1.6–1.8 V) redox processes. Three couples, negative to SCE, are assigned to CA²⁻/CA³⁻ (−0.2 to −0.3 V), and azo reductions (−0.5 to −0.7, −0.8 to −0.9 V) of the chelated R-aai-R′.