Novel Copper(II) Complexes with Dipinodiazafluorene Ligands: Synthesis,Structure, Magnetic and Catalytic Properties

The reactions of CuX₂ (X = Cl, Br) with dipinodiazafluorenes yielded four new complexes [CuX₂L₁]₂ (X = Cl (1), Br (2), L₁ = (1R,3R,8R,10R)-2,2,9,9-Tetramethyl-3,4,7,8,9,10-hexahydro-1H-1,3:8,10-dimethanocyclopenta [1,2-b:5,4-b’]diquinolin-12(2H)-one) and [(CuX₂)₂L₂]n (X = Cl (3), Br (4), L₂ = (1R,3R,8R,10R,1’R,3’R,8’R,10’R)-2,2,2’,2’,9,9,9’,9’-Octamethyl-1,1’,2,2’,3,3’,4,4’,7,7’,8,8’,9,9’,10,10’-hexadecahydro-1,3:1’,3’:8,10:8’,10’-tetramethano-12,12’-bi(cyclopenta [1,2-b:5,4-b’]diquinolinylidene). The complexes were characterized by IR and EPR spectroscopy, HR-ESI-MS and elemental analysis. The crystal structures of compounds 1, 2 and 4 were determined by X-ray diffraction (XRD) analysis. Complexes 1–2 have a monomeric structure, while complex 4 has a polymeric structure due to additional coordinating N,N sites in L₂. All complexes contain a binuclear fragment {Cu₂(μ-X)_2×2} (X = Cl, Br) in their structures. Each copper atom has a distorted square-pyramidal coordination environment formed by two nitrogen atoms and three halogen atoms. The Cu-N_ax distance is elongated compared to Cu-N_eq. The EPR spectra of compounds 1–4 in CH₃CN confirm their paramagnetic nature due to the d⁹ electronic configuration of the copper(II) ion. The magnetic properties of all compounds were studied by the method of static magnetic susceptibility. For complexes 1 and 2, the effective magnetic moments are µ_eff ≈ 1.87 and 1.83 µ_B (per each Cu²⁺ ion), respectively, in the temperature range 50–300 K, which are close to the theoretical spin value (1.73 µ_B). Ferromagnetic exchange interactions between Cu(II) ions inside {Cu₂(μ-X)₂X₂} (X = Cl, Br) dimers (J/k_B ≈ 25 and 31 K for 1 and 2, respectively) or between dimers (θ′ ≈ 0.30 and 0.47 K for 1 and 2, respectively) were found at low temperatures. For compounds 3 and 4, the magnetic susceptibility is well described by the Curie–Weiss law in the temperature range 1.77–300 K with µ_eff ≈ 1.72 and 1.70 µ_B for 3 and 4, respectively, and weak antiferromagnetic interactions (θ ≈ −0.4 K for 3 and −0.65 K for 4). Complexes 1–4 exhibit high catalytic activity in the oxidation of alkanes and alcohols with peroxides. The maximum yield of cyclohexane oxidation products reached 50% (complex 3). Based on the data on the study of regio- and bond-selectivity, it was concluded that hydroxyl radicals play a decisive role in the oxidation reaction. The initial products in reactions with alkanes are alkyl hydroperoxides.     

Cyclometalated Platinum(II) Complexes with Nitrile and Isocyanide Ligands: Synthesis,Structure, and Photophysical Properties

Russian Journal of General Chemistry - A series of cyclometalated platinum(II) complexes with nitrile and isocyanide ligands (RCN and RNC; R = t-Bu, Bn, Ph) have been synthesized in 60–80%...     

Synthesis and Characterization of Novel Trans-Mixed Diamine Platinum(II) and Platinum(IV) Complexes

A series of novel trans-mixed diamine platinum(II) and platinum(IV) complexes of type trans-[Pt^II(R-NH₂)(R'-NH₂)Cl₂] and trans -[Pt^IV(R-NH₂)(R'-NH₂)Cl₄] (where R-NH₂ = ethylamine or butylamine and R'-NH₂ = methylamine, propylamine, isopropylamine, pentylamine, or hexylamine) was synthesized and characterized using elemental analysis and infrared and ¹⁹⁵Pt nuclear magnetic resonance spectroscopic techniques.     

新型Zn(Ⅱ)和Co(Ⅱ)配合物的合成、表征及性能

以4,4'-联苯二羧酸（H₂BPDC）和4,4'-联吡啶（BPY）作为混合有机配体,Zn(II)或Co(II)作为中心金属离子,通过溶剂热法合成了两种新型配合物[Zn₃(bpdc)₃bpy]_n（1, CCDC: 1843824）和[Co₃(bpdc)₃bpy]_n（2, CCDC: 1887332）,其结构和性能经X-射线单晶衍射、红外光谱（FT-IR）、粉末X-射线衍射（PXRD）、热重分析（TG）和N₂吸附/脱附测试表征。结果表明:两种配合物具有相似的三维孔状结构,由Zn(II)或Co(II)以四配位和六配位呈现四面体和八面体空间几何构型;1和2均具有较好的热稳定性;在77 K,氮气吸附条件下,配合物1的BET比表面积为5.584 m²/g,吸附总孔体积为0.024 cm³/g,吸附平均孔径为13.932 nm。      

Zinc(II) and Nickel(II) Complexes Based on Schiff Base Ligands: Synthesis,Crystal Structure,Luminescent and Magnetic Properties

Three new phenolate oxygen bridged transition metal complexes [Zn₃(HL¹)₃(μ₃‐CH₃O)]·(ClO₄)₂(H₂O)₃ ( 1 ), [Ni₂(HL¹)₂(μ_1,1‐N₃)(o‐vanillin)]·H₂O ( 2 ), [Ni₃(HL²)₂(PhCOO)₂(PhCOOH)₂(EtOH)₂] ( 3 ) have been synthesized by metal ions and potentially multidentate Schiff base ligands (H₂L¹ = 2‐((1‐hydroxy‐2‐methylpropan‐2‐ylimino) methyl)‐6‐methoxyphenol; H₃L² = (E)‐1‐((2‐hydroxy‐3‐methoxy‐benzylidene)amino)ethane‐1,2‐diol). All the three complexes 1 , 2 , and 3 have been characterized by elemental analysis, FT‐IR spectroscopy, and single‐crystal X‐ray diffraction studies. Crystal structures reveal that complex 1 is a trinuclear incomplete cubane‐like zinc cluster whereas complex 2 is a dinuclear nickel complex bridged by azide, and compound 3 is a trinuclear nickel complex. The luminescent property for complex 1 and magnetic behaviors for complexes 2 and 3 have been investigated.     

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:     

Synthesis,Characterization and Solvatochromism Investigation of Mixed Ligand Chelate Copper(II) Complexes with Acetyleacetonate and Three Diamine Ligands

The syntheses of three mixed ligand chelate copper(II) complexes of the type [Cu(L)(acac)(H₂O)]BPh₄ where acac=acetyleacetonate; L=N,N‐dimethyl,N′‐benzylethane‐1,2‐diamine ( L¹ ), N,N‐dimethyl, N′‐2‐methylbenzylethane‐1,2‐diamine ( L² ) or N,N‐dimethyl,N′‐2‐chlorobenzylethane‐1,2‐diamine ( L³ ) are reported and characterized by elemental analyses, spectroscopic and molar conductance measurements. The X‐ray structure of complex 1 shows that the central copper atom is placed in a distorted square pyramidal geometry made by acac and diamine chelate in the base and a H₂O molecule on the apex. The prepared complexes are fairly soluble in a large number of organic solvents and show positive solvatochromism. Calculations of SMLR (stepwise multiple linear regression) method was utilized to find the best model explaining the observed solvatochromic behavior and showed that among different solvent parameters, donor number (DN) is a dominant factor responsible for the shift in the d‐d absorption band of the complexes to the lower wavenumber with increasing its values. The importance of substituent effect in diamine ligand on the spectral and SMLR measurements is also discussed.     

Synthesis,Characterization, and Structure of Metal(II) (-)-Sparteine Complexes Containing Acetate Ligands

The complexes [Co(C₁₅H₂₆N₂)(C₂H₃O₂)₂] (1), [Ni(C₁₅H₂₆N₂)(C₂H₃O₂)₂] (2), [Cu(C₁₅H₂₆N₂)(C₂H₃O₂)₂] (3) and [Zn(C₁₅H₂₆N₂)(C₂H₃O₂)₂] (4) were prepared from reaction of (?)-sparteine with the corresponding metal(II) acetates in ethanol at stoichiometric ligand to metal ratios. The complexes were characterized by UV-Vis and IR spectroscopies, and magnetic susceptibility measurements. The solid-state structures of 1, 2 and 4 have been determined by X-ray crystallography. The Complexes 1 and 2 display a pseudo-octahedral structure around the metal center, where two acetate ligands coordinate to the metal center in a bidentate fashion, whereas the metal centers in 3 and 4 adopt a pseudo-tetrahedral structure and two acetate ligands in these complexes coordinate to the metal center in a monodentate fashion. The whole set of prepared complexes has been used for comparative structural and spectroscopic studies.     

Synthesis, Crystal Structure and Properties of Polyamine Copper(II) Complexes

Two polyamine copper(II) complexes were synthesized by the reaction between N,N,N′,N′-tetrakis(2′-aminoethyl)propane-1,2-diamine hexahydrochloride and copper(II) perchlorate under almost the same conditions except for reaction temperature. The crystal structures of two complexes were determined by X-ray diffraction techniques, which shows that one of the complexes is unexpected and is a double chlorine or chloride-bridged dinuclear copper(II) complex formed by two diethylenetriamines, and another is a pentadentate mononuclear copper(II) complex composed of homo-protonated N,N,N′,N′-tetrakis(2′-aminoethyl)propane-1,2-diamine. The mechanism of the reaction leading to form the unexpected complex was discussed. The UV-visible spectra and cyclic voltammogram of the complexes were measured.     

新型苯并咪唑类配体配合物的合成及其性能

以苯并咪唑（HL¹）和3,6 二氯哒嗪在钠催化下反应制得配体3-氯-6-(苯并咪唑-1-基)哒嗪(L²）;采用溶液法和水热法,L¹分别与含有银、铜过渡金属盐反应合成了3种新的有机金属苯并咪唑配合物［AgL¹］_n(1),［Cu₄(HL¹)₄(O)(Cl)₆］(2)和{［Cu(HL¹)₂］·SiF₆}(3);采用溶液法,L²与Zn(NO₃)₂·6H₂O经配位反应合成了配合物{［Zn(L²)₃(NO₃)］NO₃}(4),其结构经IR,元素分析和X-射线单晶衍射表征。结果表明：1通过苯并咪唑桥连形成一维链状结构,2由苯并咪唑和氯离子桥接形成四核结构,3和4均显示一个单核结构,3的金属中心原子采用二配位构型,4的金属中心原子采用四配位构型。此外,研究了配体HL¹与1,及配体L²与4的荧光性能。结果表明：与HL¹相比,1的最大发射波长发生了红移;而4相对于配体L²其最大发射峰发生明显蓝移。     

Nickel(II) Complexes with Mono(imino)pyrrole Ligands: Preparation,Structure, and MMA Polymerization Behavior

Russian Journal of Coordination Chemistry - A simplified synthetic method was initiated to prepare the corresponding nickel complexes NiL2 (I–III) with direct condensation of...     

Novel Oxidovanadium Complexes with Redox-Active R-Mian and R-Bian Ligands: Synthesis,Structure, Redox and Catalytic Properties

A new monoiminoacenaphthenone 3,5-(CF₃)₂C₆H₃-mian (complex 2) was synthesized and further exploited, along with the already known monoiminoacenaphthenone dpp-mian, to obtain oxidovanadium(IV) complexes [VOCl₂(dpp-mian)(CH₃CN)] (3) and [VOCl(3,5-(CF₃)₂C₆H₃-bian)(H₂O)][VOCl₃(3,5-(CF₃)₂C₆H₃-bian)]·2.85DME (4) from [VOCl₂(CH₃CN)₂(H₂O)] (1) or [VCl₃(THF)₃]. The structure of all compounds was determined using X-ray structural analysis. The vanadium atom in these structures has an octahedral coordination environment. Complex 4 has an unexpected structure. Firstly, it contains 3,5-(CF₃)₂C₆H₃-bian instead of 3,5-(CF₃)₂C₆H₃-mian. Secondly, it has a binuclear structure, in contrast to 3, in which two oxovanadium parts are linked to each other through V=O···V interaction. This interaction is non-covalent in origin, according to DFT calculations. In structures 2 and 3, non-covalent π-π staking interactions between acenaphthene moieties of the neighboring molecules (distances are 3.36–3.40 Å) with an estimated energy of 3 kcal/mol were also found. The redox properties of the obtained compounds were studied using cyclic voltammetry in solution. In all cases, the reduction processes initiated by the redox-active nature of the mian or bian ligand were identified. The paramagnetic nature of complexes 3 and 4 has been proven by EPR spectroscopy. Complexes 3 and 4 exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. The yields of products of cyclohexane oxidation were 43% (complex 3) and 27% (complex 4). Based on the data regarding the study of regio- and bond-selectivity, it was concluded that hydroxyl radicals play the most crucial role in the reaction. The initial products in the reactions with alkanes are alkyl hydroperoxides, which are easily reduced to their corresponding alcohols by the action of triphenylphosphine (PPh₃). According to the DFT calculations, the difference in the catalytic activity of 3 and 4 is most likely associated with a different mechanism for the generation of ^●OH radicals. For complex 4 with electron-withdrawing CF₃ substituents at the diimine ligand, an alternative mechanism, different from Fenton’s and involving a redox-active ligand, is assumed.     

Synthesis,Crystal Structure and Luminescent Properties of a Novel Zinc(II) Complex of N-Acetyl-L-glutamic Acid and Imidazole Ligands

1 INTRODUCTION As is well known, some transition metal ions play an important role in controlling the behavior of many biological macromolecules and produce pro- found effects on their biological actions, medicine and people’s health[1～3]. Zinc is an essential com- ponent of many proteins. In the active sites of zinc enzymes, zinc is bound to the nitrogen of imidazole groups and oxygen of carboxylate groups of amino acids[4～6]. Additional interest in these proteins lies in the fact th…     

Synthesis,Structure and Solvatochromism Studies on Copper(II) Complexes Containing Ethylenediamine,Pyridine and Imidazol Ligands

Two copper(II) complexes type [Cu(en)X₂](ClO₄)₂, where en = ethylenediamine and X = pyridine, 1 or imidazol, 2 have been synthesized and prepared on the bases of elemental analysis, spectroscopic and molar conductance measurements. The X‐ray crystal analysis of these complexes demonstrated that the copper(II) ions are in square planar environments through coordination by two nitrogen atoms of the ethylenediamine and two nitrogen atoms of two pyridine or imidazol molecules and the ClO₄^‐ ions are bound weakly above and below of the molecular plane. The complexes show three ions behavior in all solvents. The complexes are soluble in various solvents and are solvatochromic. The solvatochromism of the complexes were investigated by UV‐Vis spectroscopy with different solvent parameters such as DN, AN, α and β using multiple linear regression (MLR) method. The results suggested that the DN parameter of the solvent has the most contribution to the shift of the d‐d absorption band of the complex 1 but in complex 2 the DN and β have almost similar importance in the observed variation in the shift of the ν_max values with solvent nature.     

New Complexes of Nickel(II) Containing Macrocyclic Diaminodiiminepiperazine Ligands: Synthesis and Electrochemical Properties

Complexes of Ni(ClO₄)₂ with 1,4-bis(2-aminobenzyl)piperidine (1) and 1,4-bis(2-amino-4-tertbutyl)piperidine (2) and products of their cyclization with ortho-phthalic aldehyde in methanol [NiL3][ClO₄]₂ (3) and [NiL4][ClO₄]₂ (4), respectively, are synthesized. Complexes 1 and 2 can be reduced on a platinum electrode irreversibly. Cyclic complexes 3 and 4 undergo reduction reversibly or quasi-reversibly in two or three stages. The reduction products react with n-BuI or n–BuBr (Bu = butyl) via an inner-sphere mechanism of oxidative attachment, probably, with the formation of the Ni–C bond.     

Schiff碱双核Mn配合物的合成、结构和性能研究

Five manganese complexes of Schiff base were synthesized： [Mn^Ⅳ，Ⅳ(μ-O)(Salen)]₂·DMF·H₂O (1)， [Mn^Ⅳ，Ⅳ(μ-O)(5-BrSalen)]₂·DMF·0.5H₂O (2)， {Mn^Ⅳ，Ⅳ(μ-O)[Sal(1，2-pn)]}₂·H₂O (3)， {Mn^Ⅳ，Ⅳ(μ-O)[5-Br-Sal(1，2-pn)]}₂·H₂O (4)， {Mn^Ⅳ，Ⅳ(μ-O)[5-CH₃-Sal(1，2-pn)]}₂·2H₂O (5)， and were characterized by element analysis， IR and UV-Vis spectra. The results of cyclic voltammogram show that Schiff base ligands can drop the potential of manganese and steady high oxide state of manganese. The magnetic properties of 1 and 3 have also been studied. The results show that there is a weak ferromagnetically coupling of Mn^Ⅳ₂ pair at room and low temperature， and the interactions of complex 3 are weaker than complex 1.     

硫、氮双齿配体与Cd(II)和Hg(II)配合物的合成与表征

以HMFC[(反)-肉桂酰基二茂铁缩(S)-甲基二硫代碳酰腙]与HBFC[(反)-肉桂酰基二茂铁缩(S)-苄基二硫代碳酰腙]两种Schiff碱分别与醋酸镉[Cd(OAc)2?2H2O]、醋酸汞[Hg(OAc)2]反应,合成了6个未见文献报道的配合物Cd(MFC)2?H2O,Cd(MFC)OAc,Cd(BFC)2,Hg(MFC)2,Hg(MFC)OAc,Hg(BFC)2,考察了其物理性质,并利用元素分析、IR,1HNMR及摩尔电导表征了其组成、可能结构,推断了配位过程.结果表明:这两种Schiff碱都是反式双齿配体,经烯硫醇化并失去质子后,以负硫离子与过渡金属离子形成共价键,氮原子与中心金属离子形成配位键.     

硫、氮双齿配体与Cd(II)和Hg(II)配合物的合成与表征

以HMFC[(反)-肉桂酰基二茂铁缩(S)-甲基二硫代碳酰腙]与HBFC[(反)-肉桂酰基二茂铁缩(S)-苄基二硫代碳酰腙]两种Schiff碱分别与醋酸镉[Cd(OAc)₂•2H₂O]、醋酸汞[Hg(OAc)₂]反应, 合成了6个未见文献报道的配合物Cd(MFC)₂•H₂O, Cd(MFC)•OAc, Cd(BFC)₂, Hg(MFC)₂, Hg(MFC)•OAc, Hg(BFC)₂, 考察了其物理性质, 并利用元素分析、IR, ¹H NMR及摩尔电导表征了其组成、可能结构, 推断了配位过程. 结果表明: 这两种Schiff 碱都是反式双齿配体, 经烯硫醇化并失去质子后, 以负硫离子与过渡金属离子形成共价键, 氮原子与中心金属离子形成配位键.     

Complexes of aminobenzylamines. part II. Complexes ofo-aminobenzylamine with palladium(II) and platinum(II)

Summary The reactions of K₂[MX₄] (M = Pd^II or Pt^II and X = Cl or Br) witho-aminobenzylamine (o-aba) have been studied in neutral aqueous solutions. Two types of complexes were isolated from these studies: [MLX₂] and [ML₂]X₂. Elemental analyses, conductivity measurements, i.r. and visible spectra suggest polymeric structures for [MLX₂] with the ligand,o-aba = L, acting as a bridge, and/or mononuclear structures for [ML₂]X₂.     

新型含氮配体多核铜配合物的合成、晶体结构及其性能研究

以1,10-邻菲罗啉(phen)为配体,采用溶剂蒸发法在水中分别合成了羟基桥连和氯离子桥连的两个新型的含氮配体多核铜离子配合物[Cu4(phen)4(H2O)2(OH)4·(NO3)4·2H2O(1)和Cu2(phen)2Cl4(2)],其结构经元素分析和X-射线单晶衍射表征。1属三斜晶系,空间群P-1,晶胞参数a=10.143 0(9),b=11.900 1(11),c=12.629 9(13),α=111.060(2)°,β=91.070 0(10)°,γ=110.920(2)°,Z=1,V=1 309.8(2)3,F(000)=692。2属单斜晶系,空间群Cc,晶胞参数a=9.860 9(8),b=17.852 9(13),c=13.412 3(15),β=106.583(11)°,Z=4,V=2 263.0(4)3,F(000)=1 256。用荧光光谱和热分析分别研究了1和2的荧光性质和热稳定性,结果表明:在310 nm激发波长激发下,与phen相比,1和2的荧光发射峰分别发生红移和蓝移,λem分别位于451 nm和374 nm。1和2的初始分解温度分别为298℃和300℃。