Synthesis and Crystal Structures of Novel Copper(I) Clusters with Bridging Silyl Amide Ligands

Treatment of copper(I) chloride with R₂Si(NLiPh)₂ (R = Me, Ph) in thf led to the formation of the octanuclear cluster compounds [Cu₈{(R₂Si(NPh)₂}₄] [R = Me ( 1 ), Ph ( 2 ).] Compound 1 crystallizes in the tetragonal space group P4/n, with a = 1505.41(5) and c = 1911.32(7) pm. The X‐ray crystal structure determination revealed a cube shaped Cu₈ cluster core with μ₄ bridging Me₂Si(NPh)₂^2– ligands. The copper atoms display an almost linear coordination with Cu–N distances in the range of 191.1(3)–191.4(3) pm. The Cu–Cu distances are 265.7(1)–267.3(1) pm. Compound 2 forms monoclinic crystals, space group P2₁/n, with a = 1461.87(4), b = 2483.77(6), c = 2725.49(8) pm, β = 100.77(1)°. The cluster core of compound 2 consists formally of two mutually perpendicular arranged trigonal prisms, which share a common square face. Like in the case of compound 1 the square faces of the cluster core are capped by μ₄ bridging Ph₂Si(NPh)₂^2– ligands. The copper atoms adopt a nearly linear N–Cu–N coordination with Cu–N distances of 190.0(4)–195.1(4) pm. The Cu–Cu distances are 252.3(1)–305.6(1) pm.     

Structures of Dimer-of-Dimers Type Defect Cubane Tetranuclear Copper(II) Complexes with Novel Dinucleating Ligands

Only a limited number of multinucleating ligands can stably maintain multinuclear metal structures in aqueous solutions. In this study, a water-soluble dinucleating ligand, 2,6-bis{[N-(carboxylatomethyl)-N-methyl-amino]methyl}-4-methylphenolate ((sym-cmp)³⁻), was prepared and its copper(II) complexes were structurally characterized. Using the single-crystal X-ray diffraction method, their dimer-of-dimers type defect cubane tetranuclear copper(II) structures were characterized for [Cu₄(sym-cmp)₂Cl₂(H₂O)₂] and [Cu₄(sym-cmp)₂(CH₃O)₂(CH₃OH)₂]. In the complexes, each copper(II) ion has a five-coordinate square-pyramidal coordination geometry. The coordination bond character was confirmed by the density functional theory (DFT) calculation on the basis of the crystal structure, whereby we found the bonding and anti-bonding molecular orbitals. From the cryomagnetic measurement and the magnetic analysis, overall antiferromagnetic interaction was observed, and this magnetic behavior is also explained by the DFT result. Judging from the molar conductance and the electronic spectra, the bridging chlorido ligand dissociates in water, but the dinuclear copper(II) structure was found to be maintained in an aqueous solution. In conclusion, the tetranuclear copper(II) structures were crystallographically characterized, and the dinuclear copper(II) structures were found to be stabilized even in an aqueous solution.     

Copper(I) Coordination Polymers with Alkanedithiol and ‐dinitrile Bridging Ligands

CuI‐based coordination polymers with 1, 2‐ethanedithiol, 3, 6‐dioxa‐1, 8‐octanedithiol and 3‐oxa‐1, 5‐pentanedinitrile as respectively μ‐S, S′ and μ‐N, N′ bridging ligands have been prepared by reaction of CuI with the appropriate alkane derivative in acetonitrile. equation/tex2gif-stack-1.gif[Cu(HSCH₂CH₂SH)₂]I ( 1 ) contains 4⁴ cationic nets, equation/tex2gif-stack-2.gif[(CuI)₂(HSCH₂CH₂OCH₂CH₂OCH₂CH₂SH)] ( 2 ) neutral layers in which stairlike CuI double chains are linked by dithiol spacers. In contrast to these 2D polymers, equation/tex2gif-stack-3.gif[CuI(NCCH₂CH₂OCH₂CH₂CN)] ( 3 ) and equation/tex2gif-stack-4.gif[(CuI)₄(NCCH₂CH₂OCH₂CH₂CN)₂] ( 4 ) both contain infinite chains with respectively (CuI)₂ rings and distorted (CuI)₄ cubes as building units. Solvothermal reaction of CuI with the thiacrown ether 1, 4, 10‐trithia‐15‐crown‐5 (1, 4, 10TT15C5) in acetonitrile affords the lamellar coordination polymer equation/tex2gif-stack-5.gif[(CuI)₃(1, 4, 10TT15C5)] ( 7 ) in which copper atoms of individual CuI double chains are bridged in a μ‐S1, S4 manner. The third sulphur atom S10 of the thiacrown ether coordinates a copper(I) atom from a parallel chain to generate a 2D network.     

Hydrothermal Synthesis and Characterization of a One-Dimensional Copper(I) Halide Cluster with 1,10-Phenanthroline

ＩｎｔｒｏｄｕｃｔｉｏｎＣｏｐｐｅｒ(Ｉ)ｈａｌｉｄｅｓｃａｎｆｏｒｍｏｌｉｇｏｍｅｒｉｃ (ｎｏｒｍａｌｌｙｄｉｍｅｒｓｏｒｔｅｔｒａｍｅｒｓ)ａｎｄｐｏｌｙｍｅｒｉｃｆｒａｍｅｗｏｒｋｓｔｈｅｍ ｓｅｌｖｅｓ .Ａｌｌｔｈｅｃｏｐｐｅｒ(Ｉ)ｈａｌｉｄｅｐｏｌｙｍｅｒｉｃｓｐｅｃｉｅｓａｒｅｂａｓｅｄｏｎｏｎｅ ｄｉｍｅｎｓｉｏｎａｌｃｈａｉｎｓ ,ｎｏｅｘａｍｐｌｅｓｏｆｔｗｏ ｄｉ ｍｅｎｓｉｏｎａｌｓｈｅｅｔｓｈａｖｅｂｅｅｎｆｏｕｎｄｓｏｆａｒ .Ｉｎｏｒｄｅｒｔｏｉｎ ｃｒｅａｓｅｔｈｅｄｉｍｅｎｓ…     

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.     

含双二苯基膦甲烷双核铜(I)配合物的合成及性质

利用配体取代反应合成了四种含双二苯基膦甲烷(dppm)的双铜(Ⅰ)配合物[Cu2(dppm)2L2](NO3)2(配体L分别是2,2'-联吡啶(1)、邻菲咯啉(2)、2,9-二甲基-邻菲咯啉(3)、吡啶(4)],并经核磁、热分析、光电子能谱等方法表征了配合物的性质.配合物(1)的晶体结构显示,dppm作为桥式双齿配体、联吡啶作为双齿配体分别与铜原子形成四面体配位结构,硝酸根离子位于配合物外界.     

Tetranuclear, Oxygen Centered Copper(II) Clusters Linked Together with Guanidine-Guanidinate Ligands

The reaction of copper(I) chloride with Htbo (1,4,6-triazabicyclo[3.3.0]oct-4-ene) under reflux in THF with oxidation by oxygen, produces a neutral cluster comprising two oxo-tetra-copper(II) units connected by six tbo⁻ bridges three of them bind two and the other three bind four metals; each unit also contains three chlorine bridges and a Htbo terminal ligand. Two different X-ray crystal structures (1a, 1b) have been determined and the magnetic behavior has been studied. The molar magnetic susceptibility measurements indicate strong exchange interactions within an oxo cluster with coupling constants of J ₁ = −163 cm⁻¹ and J ₂ = −1.1 cm⁻¹, and a weak interaction across the guanidinate bridges of J ₃ = −5.2 cm⁻¹ of the octa-Cu^II cluster.     

Insights into Structure and Biological Activity of Copper(II) and Zinc(II) Complexes with Triazolopyrimidine Ligands

In an attempt to increase the biological activity of the 1,2,4-triazolo[1,5-a]pyrimidine scaffold through complexation with essential metal ions, the complexes trans-[Cu(mptp)₂Cl₂] (1), [Zn(mptp)Cl₂(DMSO)] (2) (mptp: 5-methyl-7-phenyl-1,2,4-triazolo[1,5-a]pyrimidine), [Cu₂(dmtp)₄Cl₄]·2H₂O (3) and [Zn(dmtp)₂Cl₂] (4) (dmtp: 5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine), were synthesized and characterized as new antiproliferative and antimicrobial species. Both complexes (1) and (2) crystallize in the P2₁/n monoclinic space group, with the tetrahedral surroundings generating a square-planar stereochemistry in the Cu(II) complex and a tetrahedral stereochemistry in the Zn(II) species. The mononuclear units are interconnected in a supramolecular network through π–π interactions between the pyrimidine moiety and the phenyl ring in (1) while supramolecular chains resulting from C-H∙∙∙π interactions were observed in (2). All complexes exhibit an antiproliferative effect against B16 tumor cells and improved antibacterial and antifungal activities compared to the free ligands. Complex (3) displays the best antimicrobial activity against all four tested strains, both in the planktonic and biofilm-embedded states, which can be correlated to its stronger DNA-binding and nuclease-activity traits.     

Luminescent Tetranuclear Copper（I） Phenylacetylide Complex with Cyclohexyl Isocyanide

1INTRODUCTIONThechemistryofmetalalkynylcomplexeshasattractedmuchattentioninrecentyearsduetothespecificinterestinstructuraltopologyandopticalproperties[1～6].Ithasbeendemonstratedthatoneofthefeasiblestrategiestoattainoligomericmetalalky-nylcomplexesistodepolymerizepolymericspeciesofmetalalkynylsbyusingorganicligandssuchasphosphines[7～11]andisocyanides[12～14].Insomecases,simplemetal-containingcomponentsarealsoavail-abletodepolymerizethepolymericmetalalkynyl,formingalkynyl-bridgedheterometa…     

Biological Activity of Triazolopyrimidine Copper(II) Complexes Modulated by an Auxiliary N-N-Chelating Heterocycle Ligands

Novel complexes of type [Cu(N-N)(dmtp)₂(OH₂)](ClO₄)₂·dmtp ((1) N-N: 2,2′-bipyridine; (2) L: 1,10-phenantroline and dmtp: 5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine) were designed in order to obtain biologically active compounds. Complexes were characterized as mononuclear species that crystallized in the space group P-1 of the triclinic system with a square pyramidal geometry around the copper (II). In addition to the antiproliferative effect on murine melanoma B16 cells, complex (1) exhibited low toxicity on normal BJ cells and did not affect membrane integrity. Complex (2) proved to be a more potent antimicrobial in comparison with (1), but both compounds were more active in comparison with dmtp—both against planktonic cells and biofilms. A stronger antimicrobial and antibiofilm effect was noticed against the Gram-positive strains, including methicillin-resistant Staphylococcus aureus (MRSA). Both electron paramagnetic resonance (EPR) and Saccharomyces cerevisiae studies indicated that the complexes were scavengers rather than reactive oxygen species promoters. Their DNA intercalating capacity was evidenced by modifications in both absorption and fluorescence spectra. Furthermore, both complexes exhibited nuclease-like activity, which increased in the presence of hydrogen peroxide.     

First Copper(I) and Silver(I) Complexes Containing Phosphanylphosphido Ligands

Three new complexes with phosphanylphosphido ligands, [Cu₄{μ₂‐P(SiMe₃)‐PtBu}₄] ( 1 ), [Ag₄{μ₂‐P(SiMe₃)‐PtBu₂}₄] ( 2 ) and [Cu{η¹‐P(SiMe₃)‐PiPr₂}₂]^–[Li(Diglyme)₂]⁺ ( 3 ) were synthesized and structurally characterized by X‐ray diffraction, NMR spectroscopy, and elemental analysis. Complexes 1 and 2 were obtained in the reactions of lithium derivative of diphosphane tBu₂P‐P(SiMe₃)Li · 2.7THF with CuCl and [iBu₃PAgCl]₄, respectively. The X‐ray diffraction analysis revealed that the complexes 1 and 2 present macrocyclic, tetrameric form with Cu₄P₄ and Ag₄P₄ core. Complex 3 was prepared in the reaction of CuCl with a different derivative of lithiated diphosphane iPr₂P‐P(SiMe₃)Li · 2(Diglyme). Surprisingly, the X‐ray analysis of 3 revealed that in this reaction instead of the tetramer the monomeric form, ionic complex [Cu{η¹‐P(SiMe₃)‐PiPr₂}₂]^–[Li(Diglyme)₂]⁺ was formed.     

Synthesis of Copper(I) Complexes with Ketimide and Hydrazide Ligands

Copper(I) chloride reacted with lithium ketimides to form tetrameric homoleptic copper(I) ketimide complexes, [Cu(N=CR₂)]₄, where R = t-Bu or Ph. Mesityl copper reacted with excess 1-trimethylsilylmethyl-2,2,-dimethylhydrazine to give the mixed ligand complex (2,4,6-C₆Me₃H₂)Cu₄[N(SiMe₃)NMe₂]₃. Single-crystal X-ray crystallographic studies revealed that the three complexes have eight-member ring structures in which the ring has a hinged or butterfly shape. Although an eight-member ring structure is common for copper(I) amido, alkyl, and aryl clusters, the structure of [Cu(N=C-t-Bu₂)]₄ is unusual because the hinge angle is significantly smaller than is common, resulting in short Cu···Cu contacts compared to related complexes.     

One Novel Tetranuclear Copper Cluster by 2-(1H-Pyrazol-3-yl)pyridine:Synthesis,Structure and Properties

A novel tetranuclear copper cluster [Cu_4(μ-L)_6Cl_2] was constructed by 2-(1H-pyrazol-3-yl) pyridine(HL) under hydrothermal conditions,and structurally concluded by single-crystal X-ray diffractions,elemental analyses and IR spectra.The title complex 1 was of triclinic system,space group ■,C_(24)H_(18)ClCu_2 N_9,M_r=595.01,a=9.6497(13),b=11.4133(7),c=13.0919(15) ?,α=99.166(7),β=108.707(11),γ=111.974(9)°,V=1200.7(2)?~3,Z=2,D_c=1.997 g/cm~3,F(000)=706,μ(MoKα)=3.203 nm~(-1),R_(int)=0.0404,R=0.0536 and wR=0.1490 for4890 observed reflections with I 2σ(I).In this structure,complex 1 was the unimolecule with unprecedented tetranuclear cluster,which was expanded into a 2D network by wide-ranging C-H…Cl intermolecular hydrogen bonds and further exhibited a 3D supramolecular architecture based on π-π stacking interactions.In addition,the complex was thermally stable up to 300℃ and the solid state fluorescent property of 1 was examined and compared with the ligand.     

Tetranuclear Gold(I) Clusters with Nitrogen Donor Ligands: Luminescence and X-Ray Structure of Gold(I) Naphthyl Amidinate Complex

The syntheses and characterization of gold(I) naphthyl, pentafluorophenyl, and trifluoromethylphenyl amidinate complexes are reported. The tetranuclear clusters are obtained from the reaction of Au(tetrahydrothiophene)Cl with the potassium salt of the corresponding amidinate in a THF solvent. The crystal structures of the gold(I) naphthyl, 2, and pentafluorophenyl, 3, amidinates show a short Au···Au distance of ~3. 0 Å typical of compounds having an aurophilic interaction. The gold atoms are arranged in a square (Au···Au···Au = 87°–92°) in the pentafluorophenyl derivative and in a parallelogram (Au···Au···Au = 68°–110°) in the naphthyl amidinate complexes. The naphthyl and trifluoromethylphenyl complexes are visibly luminescent in the solid state at liquid nitrogen temperature displaying asymmetric emission bands at 538 and 473 nm, respectively. The luminescent lifetimes of these species are in the millisecond range indicating phosphorescent processes.     

Hydrothermal Synthesis and Characterization of a One—Dimen—sional Copper（Ⅰ） Halide Cluster with 1,10—Phenanthroline

The title compound Cu₂Cl₂phen (phen = 1,10‐phenanthroline, C₁₂H₈N₂) 1 was synthesized from CuCl₂·2H₂O, CuCl and phen by hydrothermal method and its structure was determined by single crystal X‐ray analysis. With phen, CuG forms one‐dimensional chains, which comprise two zigzag chains based on fused Cu‐X units and connected via covalent bonds. The compound contains two crystallographically unique monovalent copper ions, Cu(1) and Cu(2). The Cu(1) atom in the tetrahedral site, is coordinated to two bridging Cl^? and two N atoms in phen. The Cu(2) atom with a slightly distorted triangular planar geometry, is coordinated to three Cl^?. The compound 1 was crystallized in monoclinic, space group P2₁/n with a = 0.37338(4), b = 1.9510(2), c = 1.68008(19) nm, β = 95.605 (3)°, R = 0.0458, and was characterized by elemental analysis, IR spectrum and TGA analysis.     

Tetranuclear Copper(I) Complex Containing Bis (Diphenylphosphino) Methane Bridging Ligands. Crystal Structure of [Cu 4 (C 7 H 4 NO 4 ) 2 (dppm) 4 ] (NO 3 ) 2

The tetranuclear copper complex [Cu 4 (C 7 H 4 NO 4 ) 2 (dppm) 4 ] (NO 3 ) 2 (C 7 H 4 NO 4 =pyridine-2, 6-dicarboxylic acid) has been synthesized and characterized spectroscopically. The compound crystallizes in the triclinic space group $P{\bar 1}$     

Structure and Magnetic Properties of a Tetranuclear Copper(Ⅱ) Cluster Containing Dissymmetrical Oxamidate Ligand

<正>A new tetranuclear copper(II) compound containing dissymmetrical oxamidate ligand was synthesized and structurally characterized by IR spectroscopy, elemental analysis, single-crystal X-ray diffraction, and magnetic properties. The title compound 1 crystallizes in triclinic, space group P_1~- with a = 8.9547(9), b = 11.7018(9), c = 12.0288(10), α = 110.1790(10), β = 100.0700(10), γ = 100.6780(10)°, V = 1122.97(17) ~3, C_(34)H_(48)C_(l2)Cu_4N_(10)O_(16), M_r = 1177.92, D_c = 1.742 g/cm~3, μ(MoKα) = 2.067 mm~(-1), F(000) = 600, Z = 1, the final R = 0.0391 and wR = 0.1073 for 3904 observed reflections (I > 2σ(I)). In the structure, complex 1 consists of a tetranuclear unit and two perchlorate anions. Furthermore, its magnetic properties have also been investigated.