Syntheses of Binuclear Copper(I) Complexes Containing Benzimidazole

1 INTRODUCTION Procedures to synthesize copper(I) complexes are of great interest due to the diversity of products resulting from almost the same methodology. It has been long known that four-electron-donordipho- sphine compounds Ph2P(CH2)nPPh2 are excellent bi- dentate ligands[1, 2]. The chelating tendency of bis- (diphenylphosphino) methane is one of the dipho- sphine ligands most suitable to lock two metal atoms together in close proximity[3]. Many examples of bi- or polynuclear com…     

Syntheses of Binuclear Copper(Ⅰ)Complexes Containing Benzimidazole

A binuclear copper(Ⅰ) complex [Cu2(dppm)2(C7H6N2)2](NO3)2 (C7H6N2 = benzimidazole, dppm = Ph2PCH2PPh2) has been synthesized and characterized by X-ray crystallography.The crystal belongs to monoclinic, space group C2/c with a = 14.167(3), b = 21.209(4), c =20.680(4) A, β = 103.93(3)°, C32H28CuN3O3P2, Mr = 628.05, Z = 8,μ = 0.868 mm-1, V = 6031 (2)(。A)3,F(000) = 2592, Dc= 1.383 g/cm3, R = 0.0593 and wR = 0.1736.A total of 5297 independent reflec tions were collected, of which 3503 were observed with I ＞ 2σ(I).The central copper atom is tri-coordinated by phosphorus atoms from bridging dppm and nitrogen atom from benzimidazole.In the coordination sphere, the bond lengths of Cu-P(1) and Cu-P(2) are 2.2607(17) and 2.2503(16)(。A),respectively and the P-Cu-P bond angle is 127.26(6)°.     

Synthesis of β-Ketoiminato Copper(II) Complexes and Their Use in Copper Deposition

The template synthesis of ethylenediamine ( 1 ) with 2-acetylcyclopentanone ( 2 ) and [Cu(OAc)₂ · H₂O] ( 5 ) produced [Cu(1-(2-cC₅H₆(O))C(Me)NCH₂)₂)] ( 6 ) in 82 % yield. Reaction of 5 with bis(benzoylacetone)diethylenetriamine ( 7 , = L H)^[1] gave [Cu(μ-OAc)( L )(H₂O)]₂ ( 8 ). The solid-state structures of 6 and 8 were determined confirming that 8 possesses intra- and intermolecular hydrogen bonds resulting in a dimer formation. The thermal behavior of 6 – 8 was studied by TG and TG-MS. Under oxygen CuO was formed, whereas under Ar Cu/Cu₂O ( 6 ) or Cu ( 8 ) was obtained. Complex 6 was used as CVD precursor for Cu and Cu-oxide deposition (substrate temp., 400–500 °C, N₂, 60 mL · min^–1; O₂, 60 mL · min^–1; pressure, 0.87–1.5 mbar). The as-obtained deposits show separated particles of different appearance at the substrate surface as evidenced by SEM. Non-volatile 8 was applied as spin-coating precursor for Cu and CuO formation [conc. 0.25 mol · L^–1; volume 0.2 mL; 3000 rpm; depos. time 2 min; heating rate 50 K · min^–1; holding time 60 min (Ar), 120 min (air) at 800 °C]. The samples on silicon consist of granulated particles (Ar) or are non-dense with a grainy topography (air). EDX and XPS measurements confirmed the formation of Cu (Ar) or CuO (O₂) with up to 13 mol-% C impurity.     

Rapid,Catalytic Hydrolysis of DNA by Copper (Ⅱ) Complexes

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Copper (I) Iodide-Catalyzed Solvent-Free Synthesis of α-Aminophosphonates

Abstract

A method for the synthesis of α-aminophosphonates through the three-component coupling reaction of aldehydes, amines, and diisopropyl phosphite using copper (I) iodide salt catalyst is demonstrated, The reaction is highly efficient, economic, and also environment friendly.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Table S1, Figures S1–S9.]

GRAPHICAL ABSTRACT      

Biomimetic Oxidation of 1-1'-Bi-2-naphthol with Copper(Ⅰ) and Copper(Ⅱ)-amine Complexes

Copper amine complexes were used to mimic oxidases in the biomimetic oxidation of organic compounds^[1]. Masahiro Noji and coworkers^[2] reported the oxidative coupling of 2-naphthol into high yield of 1,1'-bi-2-naphthol (1) by using catalytical amount of CuCl-tetramethylethylenediamine complex at the presence of O₂. Here we report the catalytic oxidation of 1 with copper amine complexes.     

Synthesis and Characterization of Aryl Acylguanidines and Their Copper(Ⅱ) Complexes

A series of eight N-mono-substituted aryl acylguanidines L~(1～8) were synthesized from the reactions of their parent acylthioureas and respective primary amines, including five R~1C(O)N=C(NHR~2)_2 with balanced arms(denoted as R~1–R~2–R~2: Ph–Ar'–Ar', L~1(1); Ph–Ar'–Ar', L~2(2); 1-Naph–Ar'–Ar', L~3(3); 1-Naph–Ar'–Ar', L~4(4); 2-Naph–Ar'–Ar', L`5(5); Ar' = 2,6-Me_2C_6H_3, Ar' = 2,6-iPr_2C_6H_3) and three R~1C(O)N=C(NHR~2)NHR~3 with unbalanced arms(denoted as R~1–R~2–R~3: Ph–Ar'–Ph, L~6(6); Ph–Ar' –Ph, L~7(7); Ph–Ar' –Ar', L~8(8)). Treatment of L~(1～5)(1～5) with copper acetate in a molar ratio of 2:1 in dichloromethane led to the formation of homoleptic Cu(Ⅱ) complexes trans-L_2~(n')Cu(9～13), in which the Cu(Ⅱ) center was stabilized by deprotonated ligands Ln'(n = 1～5) in the O,N-bidentate mode. When similar reactions of L~6(Ph–Ar'–Ph)(6) and L~7(Ph–Ar'–Ph)(7) that contain unbalanced arms were investigated, the Cu(Ⅱ) products trans-L_2~(6')Cu(14) and trans-L_2~(7')Cu(15) were formed by deprotonating the bulky amine groups in Ln(-NHAr' for L~6 and-NHAr' for L~7) rather than the-NHPh group. In sharp contrast, trans-L_2~(8')Cu(16) was obtained from two-arm unbalanced L~8(Ph–Ar'–Ar')(8) not by deprotonating the more bulky-NHAr' group but the relatively less bulky-NHAr' group. In a further exploration, the reaction of 1:1 mixed ligands Ln and Lm with copper acetate was found to give only homoleptic Cu(Ⅱ) complex L_2~(n')Cu instead of the heteroleptic one L~(n')CuL~(m'). The in vitro antibacterial activity of L~n was evaluated against S. aureus, E. coli and C. albicans by determining the minimum inhibitory concentrations(MICs) using Kirby-Bauer test.     

Crystal Structures of Dinuclear Copper(Ⅱ) Complexes of bis (1,4,7-triazacyclononane) Ligands Containing Rigid Bridging Groups

1INTRoDUCTIoNThesynthesesandmetalcomplexationpropertiesofbis(macrocyclic)ligandshaveattractedmuchinterestinrecentyearst1-53.Theprotonatedbis(macrocycles)havebeenusedashostsforanionicsubstratest21.Thedinuclearmetalcomplexesofbis(macrocycles)havebeenstudiedasmodelsfortheactivesitesofbimetallicmetallo-proteins('-'i.Simplifiedmodelcomplexesofthistypemayhelptoelucidatethefac-torsthatdeterminetheelectronicpropertiesandthetypeandstrengthofmagneticin-teractionsinthebio-sites.Inpreviouspapert63,wer…     

Synthesis and Crystal Structure of Cobalt(Ⅱ) and Copper(Ⅱ) Complexes Involving L-Aamino Alcohols

Two novel L-amino alcohol coordination cobalt and copper complexes I and Ⅱ were obtained separately from the direct reaction of L-plenylglycinol with Co(Ⅱ) acetate tetrahydrate in anhydrous ethanol and L-leucinol with Cu(Ⅱ) chloride dihydrate in anhydrous methanol. The structures of I and Ⅱ were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I: [Co3(C51H66N3O16)]2(OAc), monoclinic, space group P21, a = 15.022(3), b = 14.242(3), c = 28.922(6) , β = 98.944(4)o, V = 6112(2) 3, Z = 4, Dc = 1.339 g/cm3, the final R = 0.0860 for 21906 observed reflections with I 2(I). For Ⅱ: Cu2[C24H58N4O7Cl]Cl, orthorhombic, space group P212121, a = 6.1861(13), b = 20.838(4), c = 28.274(6) , V = 3644.6(13) 3, Z = 4, Dc = 1.310 g/cm3, the final R = 0.0642 for 11106 observed reflections with I 2(I). The complexes were then used to catalyze the Henry reaction and catalytic activity determined by 1H NMR.     

Synthesis and Structures of Polynuclear Copper(Ⅱ)-lanthanide(Ⅲ) Complexes with Carboxylate-bridges or Imidazolemethanol

Polynuclear mixed-metal complexes are of current interest in chemistry and are of potential application in material science. We report herewith the synthesis and crystal structures of two dinuclear copper(Ⅱ)-lanthanide(Ⅲ) complexes containing pyridinioacetate (pyb, C₅H₅N+CH₂CO₂-) or N-Methyl-2-imizazolemethanol(imoh), namely[CuLa(pyb)₅(H₂O)(C1O₄)₅·2H₂O (1) and[CuLa(imoh)₂(NO₃)₃(H₂O)₂] (2). Complexes 1 features a dinuclear CuLa cation, in which the Cu and La atoms are bridged by a tetrakis(μ₂-carboxylate) bridge, the Cu atom is coordinated in a square-pyramidal geometry with the apical position being occupied by an aqua ligan, the La atom is coordinated in a distorted square-antiprism. Complex 2 also features a dinuclear CuLa molecule, with Cu and La atoms are bridged by a di(μ₂-imidazolemethanol) bridge, the Cu atom is coordinated in plane square geometry with two N and two O atoms from two imoh, besides the two O atoms from the di(μ₂-imidazolemethanol) bridge, the La atom is complied by three chelating nitrates and two aqua ligans, to form bicapped square-antiprism geometry.     

DNA Cleavage by Copper (Ⅱ) Complexes Without added Coreactants

Thedevelopmentofreagentswhichhydrolyticallycleave11ucleicacids"lidermildconditionsiscurrentlyattractinggreatinterestillthetieldofartiticialnucleases'-'.Whilemall}lreagentshavebeedsuccessfullyapplied.toDNAhydrolysis;.illershavebeenit-c'l'ersuccesseswithDNA'duetoitsrelativel}'highh}idrolyticstabilit}"(thepseudo-firsl-orderrateconstantt'Orthenollenzymatichydrolysisofphospllodiestersisextropolatedtobe2x10-"'h-=at24tandPH7.4').Theexceptionalstabilit}fofphosphodiestershasbeensuggestedasonereason…     

Complexes of tetracyanobiimidazole—V. Self-association of Ir(I) complex anions

The self-association of the planar anion [Ir(CO)₂Tcbiim]⁻ where H₂Tcbiim is 4,4′,5,5′-tetracyano-2,2′-biimidazole has been studied in acetontrile solution by analysis of the charge-transfer spectra. At low concentrations (∼ 10⁻⁵ M) monomer units prevail. At intermediate concentrations (∼ 10⁻³ M) dimerization is evident and a very strong (ε = 18 500 M⁻¹ cm⁻¹) new absorption appears at 475 nm. A novel procedure was used to obtain this value and to estimate the equilibrium constant for dimerization, 13.2 M⁻¹ at 24.4°C. From the temperature dependence of the spectra, ΔH is calculated to be −28 to −30 kJ M⁻¹. At higher concentrations (∼ 10⁻² M) spectral changes consistent with further oligomerization are observed.     

Synthesis, Structure and Magnetic Properties of Two New Homotrinuclear Bis(oxamato) Copper(II) Complexes

ＩｎｔｒｏｄｕｃｔｉｏｎＭｏｌｅｃｕｌａｒｍａｇｎｅｔｉｓｍｏｆｐｏｌｙｎｕｃｌｅａｒｃｏｍｐｌｅｘｅｓｉｓｏｆｃｏｎｓｉｄｅｒａｂｌｅｉｎｔｅｒｅｓｔｆｏｒｄｅｓｉｇｎｉｎｇｎｅｗｍａｇｎｅｔｉｃｍａｔｅｒｉａｌｓａｎｄｆｏｒｉｎｖｅｓｔｉｇａｔｉｎｇｔｈｅｒｅｌａｔｉｏｎｓｈｉｐｂｅｔｗｅｅｎｔｈｅｓｔｒｕｃｔｕｒｅａｎｄｔｈｅｒｏｌｅｏｆｔｈｅｐｏｌｙｍｅｔａｌｌｉｃａｃｔｉｖｅｓｉｔｅｓｉｎｂｉｏｌｏｇｉｃａｌｓｙｓｔｅｍｓ.1 4 Ｊｏｕｒｎａｕｘｅｔａｌ .5ｈａｖｅｒｅｃｅｎｔｌｙｐｒｏｐ…     

Syntheses,Crystal Structures and Antibacterial Activities of Schiff Base of Nickel(Ⅱ) and Copper(Ⅱ) Complexes

A new kind of Schiff base HL(HL= 1-phenyl-3-methyl-4-(p-methylbenzoyl)-5-pyrazolone with L-Leucine methyl ester) and complexes Ni L′_2·0.75C_2H_5OH·0.25H_2O,Cu L′′2(L′ = 1-phenyl-3-methyl-4-(p-methylbenzoyl)-5-pyrazolone with L-leucine ethyl,L′′ = 1-phenyl-3-methyl-4-(p-methylbenzoyl)-5-pyrazolone with L-leucine) have been synthesized and structurally determined by X-ray diffraction. For HL: crystal structure determination indicates that there are two independent HLs with different conformations in one asymmetric unit. For complex 1: the Ni(Ⅱ) ion is six-coordinated by two carbonyl oxygen atoms from pyrazolone ring,two nitrogen atoms from different HL′ and two oxygen atoms from L-Leucine ethyl ester to form a distorted octahedral geometry. For complex 2: the Cu(Ⅱ) ion is four-coordinated by one carbonyl oxygen atom from the pyrazolone ring,one nitrogen atom from HL′′,and two different carboxylic oxygen atoms from L-leucine with the same conformation to form a distorted quadrilateral geometry.     

Synthesis, Structure and Magnetic Properties of Novel Carboxylato-bridged Pentanuclear Copper(Ⅱ)-Lanthanoid(Ⅲ) Complexes

ＩｎｔｒｏｄｕｃｔｉｏｎＰｏｌｙｎｕｃｌｅａｒｍｉｘｅｄ－ｍｅｔａｌｃｏｍｐｌｅｘｅｓｃｏｎｔａｉｎｉｎｇｂｏｔｈｔｒａｎｓｉｔｉｏｎａｎｄｌａｎｔｈａｎｏｉｄｍｅｔａｌｉｏｎｓａｒｅｏｆｓｐｅｃｉａｌｃｕｒｅｎｔｉｎｔｅｒｅｓｔｉｎｒｅｌａｔｉｏｎ...     

Synthesis and Structure of the Copper(I) Complex Containing Bis(diphenylphosphino)ethane

1 INTRODUCTION Procedures to synthesize copper(I) complexes are of great interest because of the diversity of products resulting from almost the same methodology. It has long been known that four-electron-donor diphosphine compounds Ph2P(CH2)nPPh2 are excellent bidentate ligands[1]. The chelating tendency decreases as the chain length increases, so that for the ligands Ph2P(CH2)nPPh2, the tendency to chelation is the greatest for bis(diphenylphosphino)ethane. Copper(I) displays wide…     

Mechanically Activated Solid-Phase Reaction of Copper(I) Chloride with Sodium β-Diketonates: Formation of Metallic Copper Nanoparticles

Russian Journal of General Chemistry - Solid-phase reaction of copper(I) chloride with sodium β-diketonates under mechanical activation in a vibration ball mill involves disproportionation of...     

Synthesis, Characterization, Spectroscopic and Electro-chemical Properties of New Mono- and Binuclear Copper(I) Complexes with Substituted 2,2''''-Bipyridine

Introduction Copper(I) complexes have received much attention for their being less expensive and environmentally friendly, various coordination geometry, rich photo-chemical and photophysical properties.1-7 It is well known that copper complexes with diimine (2,2'-bipy- ridine, 1,10-phenanthroline and their substituted deriva-tives designated as diimine) generally exhibit low en-ergy metal-to-ligand charge-transfer (MLCT) states lo-cated in the regions of 350650 nm (e ≈ 103—104 dm3昺ol-1昪…