含双二苯基膦甲烷铜(Ⅰ)配合物的研究进展

本文概述了含双二苯基膦甲烷铜(Ⅰ)配合物的化学进展,总结了配合物的合成方法:置换法、还原法、电化学方法和直接加成法,全面论述了双核、三核、多核和异核配合物的结构特征,探讨了该类配合物的重要荧光性质。     

A Series of New Molybdenum(VI) Complexes with the ONS Donor Thiosemicarbazone Ligands

New dioxomolybdenum(VI) complexes were obtained by the reaction of [MoO₂(acac)₂] with 4‐phenylthiosemicarbazone ligands derived from salicylaldehyde, 2‐hydroxy‐1‐naphthaldehyde, 2‐hydroxy‐3‐methoxybenzaldehyde or from 4‐(diethylamino)salicylaldehyde. In all complexes the ligands are coordinated to molybdenum as tridentate ONS‐donors through phenolic‐oxygen, imine‐nitrogen and thiol‐sulphur. Octahedral coordination of each Mo atom is completed either by one neutral donor molecule (D) or by the oxygen atom of the Mo=O unit from the neighbouring molecule. All compounds were characterized by means of chemical analysis, IR spectroscopy, TG and in some cases by DSC measurements, some of them by X‐ray crystallography, and by one and two‐dimensional NMR method.     

Peroxo Complexes of Molybdenum(VI) Containing Mannich Base Ligands

The molybdenum(VI)-peroxo complexes containing Mannich base ligands having a formula as [MoO(O2)2(L-L)] [where L-L＝morpholinobenzyl benzamide (MBB), piperidinobenzyl benzamide (PBB), morpholinobenzyl urea (MBU), piperidinobenzyl urea (PBU), morpholinobenzyl thiourea (MBTU), piperdinobenzyl thiourea (PBTU)] have been synthesized and characterized by physico-chemical, electrochemical techniques and TGA/DTA studies. The complexes have been prepared by stirring ammonium molybdate and excess of 30% aqueous-H2O2 and then treatment with ethanolic solution of the ligand. Studies revealed that these complexes were non-electrolytes and diamagnetic in nature. The ligands are bound to metal in a bidentate mode through carbonyl oxygen/thiocarbonyl sulphur and the ring nitrogen. The cyclic voltammograms of the complexes show two quasi-reversible steps involving complexes. The complexes have also been tested for antibacterial activity against Salmonella and Kleibsella. The antibacterial study of the ligands and complexes indicate that the complexes exhibit higher activity than the free ligands.     

Synthesis,Structure and Characterization of Dinuclear Pentacoordinate Molybdenum(V) Complexes with Thiosemicarbazone Ligands

New dinuclear pentacoordinate molybdenum(V) complexes, [Mo₂^VO₃L₂] [L = thiosemicarbazonato ligand: C₆H₄(O)CH:NN:C(S)NHR′ and C₁₀H₆(O)CH:NN:C(S)NHR′; R′ = H, CH₃, C₆H₅) were obtained either by oxygen atom abstraction from Mo^VIO₂L with triphenylphosphine or by using [Mo₂O₃(acac)₄] in the reaction with the corresponding ligands H₂L. Crystal and molecular structure of [Mo₂O₃{C₆H₄(O)CH:NN:C(S)NHC₆H₅}₂] · CH₃CN has been determined by the single‐crystal X‐ray diffraction method.     

Synthesis and properties of novel N,C,N terdentate skeleton based on 1,3-di(pyridin-2-yl)benzene moiety-new tricks for old dogs

Utilization of intermolecular Friedel-Crafts and intramolecular condensation reaction,novel 1,3-di-(pyridine-2-yl)benzene(N,C,N terdentate) skeleton with electro-withdrawing group in 6' position of pyridyl and a cyclization between 6' position of pyridyl and 6 position of benzyl ring were firstly designed and synthesized.The structures of these novel N,C,N terdentate were confirmed by NMR,MS and X-ray single crystalanalyses.The photophysical properties of these compounds were briefly explored.     

Dinuclear Molybdenum(II) Complexes with Thioether Functionalized Silylamide Ligands

Treatment of molybdenum(II) acetate with thioether functionalized silylamides R₂Si(NLi-C₆H₄–2-SR')₂ leads to the formation of dinuclear Mo^II complexes [Mo₂{R₂Si(NC₆H₄-2-SR')₂}₂]. According to X-ray crystal structure analyses the complexes [Mo₂{Me₂Si(NC₆H₄-2-SMe)₂}₂] and [Mo₂{Ph₂Si(NC₆H₄-2-SPh)₂}₂] comprise a Mo₂-unit which is coordinated by two μ-κ-N,N' silylamide ligands. The coordination sphere around the molybdenum atoms consists of two amide nitrogen atoms and two thioether sulfur atoms in a distorted square-planar arrangement. The Mo-Mo distances are 211.0(1) and 211.7(1) pm, resp. In the complex [Mo₂{Ph₂Si(NC₆H₄-2-SMe)₂}₂] the silyl amide units act as tetradentate κ-N,N',S,S'chelating ligands and the Mo-Mo distance is 218.6(1) pm.     

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。     

新型不对称三齿多吡啶配体及其混配钌(II)配合物的合成、表征及与DNA相互作用研究

合成了两个新型不对称三齿多吡啶配体 ,3 ( 1,10 菲咯啉基 2 ) 1,2 ,4 三唑 (PHT) ,3 ( 1,10 菲咯啉基 2 ) 5 甲基 1,2 ,4 三唑 (PHMT) ,及其混配配合物 [Ru(tpy) (PHT) ] 2 + (Ru1)和 [Ru(tpy) (PHMT) ] 2 + (Ru2 ) ,通过元素分析、FAB MS ,ES MS ,1HNMR ,IR ,UV vis ,发射光谱和电化学对它们进行了表征 .运用电子吸收光谱、竞争性结合实验和粘度测试等方法研究了配合物与DNA的作用机理 ,结果显示它们均是通过静电作用与DNA结合 ,且Ru2与DNA的作用比Ru1与DNA的作用更强 .     

基于含有硫醚基团的吡啶烷基酰胺配体的铜配合物的合成和结构表征

合成和表征了含有硫醚基团的吡啶烷基酰胺配体2-(甲硫基)-N-[2-(2-吡啶)甲基]乙酰胺(HL1)和2-(甲硫基)-N-[2-(2-吡啶)乙基]乙酰胺(HL2)及其3个铜的配合物,{[Cu(L1)(CH₃OH)](OTf)}_n(1)(Otf=三氟甲磺酸根),{[Cu(L2)(OTf)]·CH₃OH}_n(2)和[Cu(HL2)(CH₃OH)Cl](3),并通过X-射线单晶衍射分析确定了其晶体结构。配合物1和2均为含有铜的一维配位聚合物,而配合物3为单核铜配合物。分析了配合物中铜离子的配位特点及可能的形成原因。     

Reactions of bis(diphenylphosphine)acetylene with metal carbonyl complexes

The reaction of [Co₂(CO)₈] with DPPA at room temperature yields a diphosphine bridged product [Co₄(CO)₁₂(μ-Ph₂-P-C≡C-P-Ph₂)₂] 1. Heating of 1 at 45°C promoted cleavage of the P-C_sp bond with the formation of binuclear, phosphido-bridged σ-π-acetylide isomer complexes [Co₂(CO)₅(μ-PPh₂) (μ-σ-π-C≡C-PPh₂ )] 2a, 2b. Heating (60°C) of the complex [CpFe(CO)₂CH₃] and DPPA affords mono and binuclear acetyl, P-coordinated diphenylphosphinoalkyne metal complexes [CpFe(Ph₂P-C≡C-PPh₂)CO(COCH₃)] 3, [CpFeCO(COCH₃)]₂-μ-(Ph₂P-C≡C-PPh₂) 4.     

基于含有硫醚基团的吡啶烷基酰胺配体的铜配合物的合成和结构表征

合成和表征了含有硫醚基团的吡啶烷基酰胺配体2-(甲硫基)-N-[2-(2-吡啶)甲基]乙酰胺(HL1)和2-(甲硫基)-N-[2-(2-吡啶)乙基]乙酰胺(HL2)及其3个铜的配合物,{[Cu(L1)(CH₃OH)](OTf)}_n(1)(Otf=三氟甲磺酸根),{[Cu(L2)(OTf)]·CH₃OH}_n(2)和[Cu(HL2)(CH₃OH)Cl](3),并通过X-射线单晶衍射分析确定了其晶体结构。配合物1和2均为含有铜的一维配位聚合物,而配合物3为单核铜配合物。分析了配合物中铜离子的配位特点及可能的形成原因。     

Luminescent Properties of Hexanuclear Molybdenum(II) Chloride Clusters Containing Thiolate Ligands

The emission spectra of a series of molybdenum(II) chloride clusters containing thiolate ligands, [Mo₆(μ₃-Cl)₈(SR)₆]²⁻ (R = Et, Bu, Ph, Bn), have been recorded. These complexes all show a broad emission at ~700 nm after excitation at 337, 400 and 410 nm. Determination of the excited state lifetimes and quantum yields of these complexes in acetonitrile reveals that (Bu₄N)₂[Mo₆(μ₃-Cl)₈(SPh)₆] displays the longest excited state lifetime of this series (26 μs at 296 K).

Conformation of the Dimethyl Maleate Ligands in a Molybdenum(0) Complex. Crystal Structure of d6 trans-Bis(Dimethyl Maleate)-Dicarbonyl-O-Phenylenediaminemolybdenum(O)

The solid-state structure of Mo(CO)₂(DMMA)₂(PDA) (DMMA = dimethyl maleate, PDA = o-phenylenediamine) was determined by X-ray diffraction of single crystal. The complex crystallizes in the hexagonal space group P₆122 with a = 11.085(5), b = 11.085(5), c = 33.653(21) Å, γ = 120°, and Z = 6. The geometry of this bis(DMMA) complex is distorted octahedral with the two CO groups cis to each other and trans to the PDA ligand and the two DMMA ligands trans to each other and cis to the two CO ligands. The orientations of the two trans DMMA ligands are mutually perpendicular and each DMMA ligand eclipses an N-Mo-CO vector. The carbon-carbon double bond of DMMA is bonded to molybdenum unsymmetrically with the olefin carbon adjacent to a coordinated amino group closer to the metal than that adjacent to a carbonyl group. The conformation of each DMMA is that the two ester groups attached to DMMA lie in the regions described by N-Mo-C and N-Mo-N. Bond-distance calculations indicate that each keto oxygen of the ester groups in the region described by N-Mo-C forms a hydrogen bond with an amino hydrogen on the PDA ligand; this hydrogen bonding is responsible for the observed conformation of the complex. The conformalion of this complex in the solid-state is in agreement with the results in solution predicted according to ¹H NMR spectral data.     

Syntheses and Characterization of Half—Sandwich Zirconium Complexes with Dichalcogenolate o—Carborane Ligands

Metallocene complex Cp2^ttZrCl2(Cp^tt=η^5-1,3-^tBu2C5H3)(1)has been prepared from the reaction of LiCp^tt with ZrCl4 in good yield.Reactions of 1 with dilithium dichalcogenolate o-carboranes afforded new type of half-sandwich compounds with dichalcogenolate o-carboranyl ligands,[Li(THF)4][Cp^ttZr(E2C2B10H10)2](E=S,2a;E=Se,2b)in which only one cyclopentadienyl ring ligand existed.Complexes 1 and 2a were structurally characterized by X-ray analyses.In complex 2a,the Zr(IV)ion is η^5-bound to one 1,3-ditert-cyclopentadienyl ring and σ-bound to four μ2-sulfur atoms of two dithio-carboranes.the zirconium atom and four sulfur atoms form a distorted pyramid.The coordination sphere around the zirconium atom resembles in a piano stool structure with four legs of sulfur stoms and the fulcrum at the zirconium stom.     

新型的含硫族元素碳硼烷配体的三(3，5-二甲基-1-吡唑)硼氢钼配合物的合成和分子结构(英)

三齿单核三(3，5-二甲基-1-吡唑)硼氢钼配合物Tp^*Mo(O)Cl₂ (1)(Tp^*=三(3，5-二甲基-1-吡唑)硼氢HB(C₃H(Me₂)N₂)₃)与含硫族元素碳硼烷的锂盐[(THF)₂LiE₂C₂B₁₀H₁₀(THF)]<     

Syntheses, Characterization and Crystal Structures of New Nickel Complexes with 2,6-Bis(imino)pyridyl Ligands

Introduction In the past decade, the imino-complexes based on late transition metal have received significantly increasing attention for their excellent performance in the olefin polymerization area since Brookhart et al.[1-8]     

Syntheses, Characterization and Crystal Structures of New Nickel Complexes with 2,6-Bis （ imino ） pyridyl Ligands

In the past decade, the imino-complexes based on late transition metal have received significantly increasing attention for their excellent performance in the olefin polymerization area since Brookhart et al. demonstrated that the Ni( Ⅱ ) complexes incorporating with sterically hindered α-diimine ligands could be used in the polymerization of ethylene to form high molecular weight polymers.     

Synthesis of new ruthenium(II) complexes derived from labile nitrile ligands: an alternative route to the preparation of trans-dichlorotetrakis(diphenylphosphine)ruthenium(II)

New ruthenium(II) complexes containing labile nitrile ligands have been prepared by treatment of either the polymer [{RuCl₂(COD)}_x] (COD = cycloocta-1,5-diene) (1) or its derivative [RuCl₂(COD)(NCCH₃)₂]·NCCH₃ (2) with the appropriate nitrile ligands in refluxing acetonitrile under argon. A new route to synthesis of trans-dichlorotetrakis(diphenylphosphine)ruthenium(II) (7) was also reported. A redetermination of the structure of 7 was undertaken and X-ray crystallographic data revealed that the complex crystallizes in the triclinic space group P-1 with unit cell dimensions a = 12.7016(9) Å, b = 13.0847(10) Å, c = 14.1498(10) Å, α = 101.46(3)°, V = 2080.6(3) Å³, Z = 2 and R = 0.0309. Its polymorph 7′ was also obtained. The crystal structure of 4 was also determined. This complex crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 27.0510(3) Å, b = 11.0984(13) Å, c = 13.0450(16) Å, α = 90°, V = 3886.5(8) Å³, Z = 8 and R = 0.0282.     

Lanthanide(III) Complexes with Pyridine Head Macrocyclic Ligands

The ability of lanthanide(III) ions to form stable complexeswith three different macrocyclic ligands, L¹ , L² and L³ , has been investigated.The Schiff base macrocycle L¹ and its corresponding reduced ligand L² arederived from 2,6-bis(2-formylphenoxymethyl)pyridine and diethylentriamine;the reduced ligand L³ is derived from 2,6-diformylpyridine and N,N-bis(3-aminopropyl)methylamine. Lanthanide nitrate complexes of L¹ and L² have beenprepared by direct reaction between each ligand and the appropriate hydrated lanthanidenitrate; attempts to obtain the corresponding perchlorate complexes have been unsuccessful.All nitrate complexes of L¹ give the expected [1:1, Ln:L¹ ] stoichiometry; however, complexes obtained with L² show a [2:1, Ln:L² ] stoichiometry. Finally, complexation reactions with L³ have been carried out in order to investigatethe coordination capability of this small and flexible ligand towards the Ln(III) ions.