Spectroscopic and Electrochemical Properties of Palladium(II) and Platinum(II) 2-(2-Pyridyl)thiophenide Complexes with 4,4'-Bipyridyl

Russian Journal of General Chemistry -     

1,2-二（二苯基膦）乙烷氯化钯(II)的合成及催化活性

以卤化钯（X=Cl、 Br、 I）为原料,乙腈为溶剂,与1,2-二（二苯基膦）乙烷反应,合成了1,2-二（二苯基膦）乙烷卤化钯[Pd(dppe)X₂, dppe=1,2-二（二苯基膦）乙烷],产率均高于96％,其结构经¹H NMR, XRD和元素分析确证。以Suzuki反应和Stille C—C偶联反应为模板反应,研究了Pd(dppe)Cl₂的催化活性。结果表明：Pd(dppe)Cl₂对2-氯噻吩和对甲氧基苯硼酸的Suzuki偶联反应、4,7-二氯苯并噻二唑核或其他含苯并噻二唑核的卤代芳烃与其他芳香核的锡试剂的Stille C—C偶联反应的催化转化率分别为80%~85%和52%~60%,催化活性优于四（三苯基膦）钯(70%~85%和43%~50%)。     

新型多吡啶铂(Ⅱ)络合物的设计、合成及性能研究

<正>由于特殊的分子构型及电子排布,具有平面四边形构型的多吡啶Pt(Ⅱ)络合物能够产生许多特殊的、具有潜在应用价值的激发态性质．本论文设计、合成了一系列以三联吡啶、6-苯基-2,2’-二联吡啶、菲啰啉为主配体,取代苯乙炔为辅助配体的多吡啶Pt(Ⅱ)络合物,系统地研究了它们的光物理性质,取得如下有意义的研究结果:     

Heteroleptic Ruthenium(II) 2,2'-Bipyridine Complexes Incorporating Bipyrazolate and 2-Pyridyl Pyrazolate Ancillaries

Russian Journal of Coordination Chemistry - Treatment of 5,5′-di(trifluoromethyl)-3,3′-bipyrazole (BipzH2) with cis-[RuCl2(Bipy)2]·2H2O (Bipy = 2,2′-bipyridine) or...     

含C16长碳链1，2－邻二萘醌－2－肟钌（Ⅱ）配合物的合成

通过三种构型的1，2－邻二萘醌－2－肟（2－nqo)钌（Ⅱ）羰基配合物trans, cis－（Ru(2-nqo)2(CO)2](1){(trans-NO,cis-O},cis-,trans-[Ru(2-nqo)2(CO)2] (2){cis-NO,trans-O}及cis,-cis-[Ru(2-nqo)2(CO)2](3){(cis-NO,cis-O)}的去羰 基取代反应，合成了含C16长碳链2-nqo钌（Ⅱ）配合物trans-,cis-[Ru(2-nqo)2 (CO)(spy)](4),cis-,trans-(Ru(2-nqo)2(CO)(spy)(5),cis-,cis-[Ru(2-nqo)2 (CO)(spy)](6)及trans-,trans-(Ru(2-nqo)2(spy)2](7){(trans-NO,trans-O)}。 对其进行了红外、紫外－可见质谱及核磁人振测试，并利用^1H-^1H偶合二维核磁 技术对核磁共振峰进行了指认。     

Palladium(II) Complexes with the 4,5-Bis(diphenylphosphino)acenaphthene Ligand and Their Reactivity with Ethylene

The last two decades have witnessed the development of homogeneous catalysts for ethylene homo- and co-polymerization reactions based on late transition metals. When Pd(II) is the metal of choice, the best ligand-metal combination deals with either bidentate nitrogen-donor molecules or phosphinobenzene sulfonate derivatives. In this contribution we have investigated the coordination chemistry to Pd(II) of a bidentate phosphorus ligand, namely 4,5-bis(diphenylphosphino)acenaphthene ( 1 ). Starting from the neutral complex, [Pd( 1 )(CH₃)Cl], we obtained the cationic derivatives [Pd( 1 )(CH₃)(L)][SbF₆], with L being either CH₃CN or 3,5-lutidine. Using in situ NMR spectroscopy we investigated the reaction of [Pd( 1 )(CH₃)(NCCH₃)][SbF₆] with ethylene, at room temperature, and ambient ethylene pressure. We discovered that [Pd( 1 )(CH₃)(NCCH₃)][SbF₆] acts as a catalyst for butenes and hexenes synthesis with the relevant Pd-ethyl intermediate as the catalyst resting state. At the same time the color of the solution turned from pale yellow to light red due to the formation of the dinuclear species [Pd(μ-η²−C₆H₅)PPh)−PPh₂]₂[SbF₆]₂. Both the neutral Pd(II) complex, activated in situ by NaSbF₆, and the monocationic acetonitrile derivative were tested in the ethylene homopolymerization reaction at high pressure, leading to low molecular weight, branched, polyethylene.     

1,2-二(2-胺基苯氧基)乙烷银配合物的合成与晶体结构

本文采用配体1, 2-二(邻氨基苯氧基)乙烷(L)分别与AgPF6, AgCF3SO3, AgNO3和AgSbF6 进行配位反应,依次得到了四个配合物1 [Ag2(L)2(PF6)]、2 [Ag2(L)2(CF3SO3)2]、3 [Ag(L)NO3]n 和4 [Ag(L)2SbF6]n,并通过FTIR、元素分析、以及X射线单晶衍射等对配合物的结构与组成进行了表征。单晶衍射结果表明,配合物1和2为双核银(I)配合物,3和4为银(I)的配位聚合物。配合物1具有穴状结构,2经Ag?Ag键桥连两个配体形成扭曲的非平面结构。聚合物3的结构为一维(1D)“之”字链,4具有三维(3D)多孔的结构框架。在四个配合物结构中,相应的抗衡阴离子均未参与Ag(I)进行配位作用。     

1,2-Bis(diphenylphosphino)ethane-containing commo-ferracarboranes of unusual structure

Russian Chemical Bulletin - commo-Ferracarboranes and [8-{(nido-7″,8″-C2B9H11-9″(11″)-)Ph2PCH2CH2PPh2}-commo-3,3′-Fe-{1,2-C2H9B10}{1′2′-C2B9H11}] were...     

1,2-二(2-甲氧基苯基)-1,2-乙二胺的制备方法研究

手性1,2-二(2-甲氧基苯基)-1,2-乙二胺可作为有机小分子催化剂、金属配体前体广泛应用于多种有机合成反应之中,其可以消旋体为原料通过拆分得到。以廉价易得的邻甲氧基苯甲醛为原料,重点针对亚胺中间体还原过程中反应条件苛刻、后处理复杂等问题,首次利用Mg作为还原剂,在室温下,以93%的分离收率得到关键中间体3。通过该关键步骤的放大实验（92%）,进一步评价了该方法的应用潜力。      

Electrochemical Polymerization of Ni(II) and Pd(II) Complexes with 1,2-Bis(o-aminobenzylidene)ethylenediamine

Polymers based on the Pd(II) and Ni(II) complexes with 1,2-bis(o-aminobenzylidene)ethylenediamine and exhibiting conducting properties are synthesized. The kinetic regularities of polymer formation on solid substrates and dependence of the rate of charge diffusion in a bulk of polymer matrix on the polymer thickness are established.     

Synthesis,Characterization and Electrochemistry of 1,2-Bis(diphenylphosphino)benzene-chelated Diiron Ethane-1,2-dithiolate Tetracarbonyl Complex

In this paper, a novel diiron ethane-1,2-dithiolate complex [Fe_2(CO)_4{κ~2-(Ph_2P)_2(1,2-C_6H_4)}(μ-SCH_2CH_2S)] has been prepared and structurally characterized. Treatment of the parent complex [Fe_2(CO)_6(μ-SCH_2CH_2S)] with 1 equivalent of 1,2-bis(diphenylphosphino)benzene and Me_3NO?2H_2O as the oxidative agent gave the title complex in good yield. The title complex has been characterized by elemental analysis, IR, ~1H NMR, ~(31)P{~1H} NMR, ~(13)C{~1H} NMR spectroscopy, and X-ray crystallography. X-ray crystal structure of the title complex contains a butterfly diiron cluster with a bridging ethane-1,2-dithiolate, four terminal carbonyls, and a chelating 1,2-bis(diphenylphosphino)benzene. In addition, electrochemical studies revealed that the title complex can catalyze the reduction of protons to H_2 in the presence of acetic acid.     

Synthesis and Physicochemical Study of Iron(II), Cobalt(II), Nickel(II), and Copper(II) Complexes with 4-(2-Pyridyl)-1,2,4-Triazole

New complexes of iron(II), cobalt(II), and nickel(II) with 4-(2-pyridyl)-1,2,4-triazole (PyTrz), [Fe₃(PyTrz)₈(H₂O)₄]A₆ (A = NO₃ ^-, ClO₄ ^-, Br^-) and [M₃(PyTrz)₈(H₂O)₄](NO₃)₆ (M = Co, Ni), were synthesized and studied by X-ray diffraction, magnetochemical method, and electronic and IR spectroscopy. The complex [Fe₃(PyTrz)₈(H₂O)₄](NO₃)₆) was also studied by adiabatic calorimetry. The Fe(II), Co(II), and Ni(II) nitrate complexes were shown to be isostructural to the previously synthesized linear trinuclear [Cu₃(PyTrz)₈H₂O)₄](NO₃)₆ complex. In all compounds, antiferromagnetic exchange interactions between M²⁺ ions were detected. The complex [Fe₃(PyTrz)₈(H₂O)₄](NO₃)₆ undergoes the ¹ A ₁ ⁵ T ₂ spin transition.     

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′.     

2,3-Bis(diphenylphosphino)-1,3-butadien

2,3-Bis(diphenylphosphino)-1,3-butadiene A method for synthesis of the title compound is described, using the readily available 2,3-bis(diphenylphosphinoyl)-1,3-butadiene ( 1 ) as the starting material. For the protection of the diene system, 1 is first converted into the 1,4-dibromo- and 1,4-dichloro derivatives 2a and b , respectively, by addition of Br₂ or Cl₂, respectively. The structure of 2b has been determined by single-crystal X-ray diffraction. The molecule has a centrosymmetrical (E)-configuration. Reduction of the phosphinoyl groups by HSiCl₃(to give the bis(diphenylphosphino)compound 3), followed by removal of the Cl-atoms using Zn powder, affords the bis(diphenylphosphino)butadiene 4 . Compounds 3 and 4 give quaternary phosphonium salts 5 and 6 , respectively, on addition of CH₃OSO₂F or CH₃I. The sulfur analogue of 1 is formed on treatment of 4 with elemental sulfur.     

Synthesis and Characterization of Water-Soluble 1,2-Bis(bis(hydroxyalkyl)phosphino)ethane Ligands and Their Nickel(II), Ruthenium(III), and Rhodium(I) Complexes

The syntheses of the water-soluble, chelating phosphines 1,2-bis(bis(hydroxybutyl)phosphino)ethane (1, n = 3; DHBuPE) and 1,2-bis(bis(hydroxypentyl)phosphino)ethane (1, n = 4; DHPePE) are reported. These ligands (and, in general, other 1,2-bis(bis(hydroxyalkyl)phosphino)ethane ligands) can be used to impart water solubility to metal complexes. As examples of this, the [Ni(DHPrPE)(2)Cl]Cl (2), [Rh(DHPrPE)(2)][Cl] (3), and [Ru(DHBuPE)(2)Cl(2)][Cl] (4) complexes were synthesized; they are indeed soluble in water (>0.5 M). Crystals of DHPrPE (1, n = 2) are monoclinic, space group P2(1)/c, with a = 9.5935(8) ?, b = 9.353(2) ?, c = 10.655(2) ?, alpha = 90 degrees, beta = 100.03(1) degrees, gamma = 90, V = 941.5(5) ?(3), R = 0.051, and Z = 2. Crystals of [Ni(DHPrPE)(2)Cl]Cl (2) are monoclinic, space group I2, with a = 15.951(3) ?, b = 11.454(2) ?, c = 20.843(3) ?, alpha = 90 degrees, beta = 91.24(2) degrees, gamma = 90 degrees, V = 3807(2) ?(3), R = 0.062, and Z = 4. Crystals of [Rh(DHPrPE)(2)][Cl] (3) are triclinic, space group P&onemacr;, with a = 13.900(2) ?, b = 15.378(2) ?, c = 18.058(2) ?, alpha = 87.71(1) degrees, beta = 75.03(1) degrees, gamma = 85.24(1), V = 3715(2) ?(3), R = 0.044, and Z = 4. Crystals of [Ru(DHBuPE)(2)Cl(2)][Cl] (4) are monoclinic, space group C2/c, with a = 14.310(2) ?, b = 21.630(2) ?, c = 15.459(3) ?, alpha = 90 degrees, beta = 99.83(1) degrees, gamma = 90, V = 4715(1) ?(3), R = 0.056, and Z = 4.