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

ＩｎｔｒｏｄｕｃｔｉｏｎＮｕｃｌｅａｓｅｓｗｈｉｃｈｃａｔａｌｙｚｅｔｈｅｈｙｄｒｏｌｙｔｉｃｃｌｅａｖａｇｅｏｆｔｈｅｐｈｏｓｐｈｏｄｉｅｓｔｅｒｂａｃｋｂｏｎｅｏｆＤＮＡａｎｄＲＮＡｐｌａｙａｎｉｍｐｏｒｔａｎｔｒｏｌｅｉｎｔｈｅｍｏｌｅｃｕｌａ...     

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      

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.     

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.     

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…     

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 Two New Homotrinuclear Bis(oxamato) Copper(II) Complexes

ＩｎｔｒｏｄｕｃｔｉｏｎＭｏｌｅｃｕｌａｒｍａｇｎｅｔｉｓｍｏｆｐｏｌｙｎｕｃｌｅａｒｃｏｍｐｌｅｘｅｓｉｓｏｆｃｏｎｓｉｄｅｒａｂｌｅｉｎｔｅｒｅｓｔｆｏｒｄｅｓｉｇｎｉｎｇｎｅｗｍａｇｎｅｔｉｃｍａｔｅｒｉａｌｓａｎｄｆｏｒｉｎｖｅｓｔｉｇａｔｉｎｇｔｈｅｒｅｌａｔｉｏｎｓｈｉｐｂｅｔｗｅｅｎｔｈｅｓｔｒｕｃｔｕｒｅａｎｄｔｈｅｒｏｌｅｏｆｔｈｅｐｏｌｙｍｅｔａｌｌｉｃａｃｔｉｖｅｓｉｔｅｓｉｎｂｉｏｌｏｇｉｃａｌｓｙｓｔｅｍｓ.1 4 Ｊｏｕｒｎａｕｘｅｔａｌ .5ｈａｖｅｒｅｃｅｎｔｌｙｐｒｏｐ…     

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…     

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

ＩｎｔｒｏｄｕｃｔｉｏｎＰｏｌｙｎｕｃｌｅａｒｍｉｘｅｄ－ｍｅｔａｌｃｏｍｐｌｅｘｅｓｃｏｎｔａｉｎｉｎｇｂｏｔｈｔｒａｎｓｉｔｉｏｎａｎｄｌａｎｔｈａｎｏｉｄｍｅｔａｌｉｏｎｓａｒｅｏｆｓｐｅｃｉａｌｃｕｒｅｎｔｉｎｔｅｒｅｓｔｉｎｒｅｌａｔｉｏｎ...     

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…     

Syntheses and Crystal Structures of Mono-and Binuclear Copper(Ⅱ) Mixed-ligand Complexes Involving Schiff Base

1 INTRODUCTION The chemistry of copper compounds has been extensively investigated and the relationship be- tween structure and reactivity, ranging from indus- trial catalysis to biochemistry activity, is of major importance. For binuclear copper(II) complexes equa- torially bridged by pair of hydroxide[1] or alkoxide[2, 3] groups, satisfactory linear correlation is found be- tween the Cu–O–Cu bridging angle and spin coupling between the metal centers. However, for binuclear copper(I…