Binuclear copper(II) complexes of xylyl-bridged bis(1,4,7-triazacyclononane) ligands

Copper(II) complexes of three bis(tacn) ligands, [Cu(2)(T(2)-o-X)Cl(4)] (1), [Cu(2)(T(2)-m-X)(H(2)O)(4)](ClO(4))(4).H(2)O.NaClO(4) (2), and [Cu(2)(T(2)-p-X)Cl(4)] (3), were prepared by reacting a Cu(II) salt and L.6HCl (2:1 ratio) in neutral aqueous solution [T(2)-o-X = 1,2-bis(1,4,7-triazacyclonon-1-ylmethyl)benzene; T(2)-m-X = 1,3-bis(1,4,7-triazacyclonon-1-ylmethyl)benzene; T(2)-p-X = 1,4-bis(1,4,7-triazacyclonon-1-ylmethyl)benzene]. Crystals of [Cu(2)(T(2)-m-X)(NPP)(mu-OH)](ClO(4)).H(2)O (4) formed at pH = 7.4 in a solution containing 2 and disodium 4-nitrophenyl phosphate (Na(2)NPP). The binuclear complexes [Cu(2)(T(2)-o-XAc(2))(H(2)O)(2)](ClO(4))(2).4H(2)O (5) and [Cu(2)(T(2)-m-XAc(2))(H(2)O)(2)](ClO(4))(2).4H(2)O (6) were obtained on addition of Cu(ClO(4))(2).6H(2)O to aqueous solutions of the bis(tetradentate) ligands T(2)-o-XAc(2) (1,2-bis((4-(carboxymethyl)-1,4,7-triazacyclonon-1-yl)methyl)benzene and T(2)-m-XAc(2) (1,3-bis((4-(carboxymethyl)-1,4,7-triazacyclonon-1-yl)methyl)benzene), respectively. In the binuclear complex, 3, three N donors from one macrocycle and two chlorides occupy the distorted square pyramidal Cu(II) coordination sphere. The complex features a long Cu...Cu separation (11.81 A) and intermolecular interactions that give rise to weak intermolecular antiferromagnetic coupling between Cu(II) centers. Complex 4 contains binuclear cations with a single hydroxo and p-nitrophenyl phosphate bridging two Cu(II) centers (Cu...Cu = 3.565(2) A). Magnetic susceptibility studies indicated the presence of strong antiferromagnetic interactions between the metal centers (J = -275 cm(-1)). Measurements of the rate of BNPP (bis(p-nitrophenyl) phosphate) hydrolysis by a number of these metal complexes revealed the greatest rate of cleavage for [Cu(2)(T(2)-o-X)(OH(2))(4)](4+) (k = 5 x 10(-6) s(-1) at pH = 7.4 and T = 50 degrees C). Notably, the mononuclear [Cu(Me(3)tacn)(OH(2))(2)](2+) complex induces a much faster rate of cleavage (k = 6 x 10(-5) s(-1) under the same conditions).     

The complexing properties of 1,4,7-tris(dihydroxyphosphorylmethyl)-1,4,7-triazacyclononane

The complexation of 1,4,7-tris(dihydroxyphosphorylmethyl)-1,4,7-triazacyclononane with metal ions, differing in both charge and ionic radius, was studied. This complexing agent is selective relative to cations of a given ionic radius. The stability of the complex increases with increasing charge and polarizability of the cation.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 917–919, April, 1990.     

New bis-cresol-bridged bis(1,4,7-triazacyclononane) ligand as receptor for metal cations and phosphate anions

The synthesis and characterization of a new bis([9]aneN3) ligand (H2L) containing two [9]aneN3 macrocyclic moieties separated by a 2,2'-methylene-bis-cresol (cresol = 4-methyl-phenol) unit is reported. A potentiometric and (1)H NMR study in aqueous solution reveals that H2L is in a zwitterionic form, and protonation of the cresolate oxygens occurs only with the formation of the highly charged (H5L)(3+) and (H6L)(4+) species at acidic pH values. The coordination properties of H2L toward Cu(II), Zn(II), Cd(II), and Pb(II) were studied by means of potentiometric and UV spectrophotometric measurements. The ligand gives both mono- and binuclear complexes in aqueous solution. At acidic pH values the ligand forms stable binuclear [M2H2L](4+) complexes, where each metal is coordinated by two amine groups of [9]aneN3 and the deprotonated oxygen of the adjacent cresol unit; the remaining amine group is protonated. Deprotonation of the [M2H2L](4+) species at alkaline pH values affords [M2L](2+) complexes, where all amine groups of the [9]aneN3 moieties are involved in metal coordination. Binding of mono-, di- and triphosphate, and adenosine triphosphate (ATP) was studied by means of potentiometric, (1)H and (31)P NMR measurements and by molecular dynamics simulations. The receptor forms stable 1:1 adducts with di-, triphosphate, and ATP, while the interaction with monophosphate is too low to be detected. In the complexes both the [9]aneN3 moieties act cooperatively in the substrate binding process. The stability of the adducts increases in the order diphosphate < triphosphate < ATP. This trend is explained in terms of increasing number of charge-charge interactions between the phosphate chains and the protonated [9]aneN3 subunits and, in the case of ATP, of stacking interactions between the adenine and cresol units.     

Kinetics and mechanism of hydrolysis of a model phosphate diester by [Cu(Me3tacn)(OH2)2]2+ (Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane)

The kinetics of hydrolysis of bis(p-nitrophenyl)phosphate (BNPP) by [Cu(Me3tacn)(OH2)2]2+ has been studied by spectrophotometrical monitoring of the release of the p-nitrophenylate ion from BNPP. The reaction was followed for up to 8000 min at constant BNPP concentration (15 microM) and ionic strength (0.15 M) and variable concentration of complex (1.0-7.5 mM) and temperature (42.5-65.0 degrees C). Biphasic kinetic traces were observed, indicating that the complex promotes the cleavage of BNPP to NPP [(p-nitrophenyl)phosphate] and then cleavage of the latter to phosphate, the two processes differing in rate by 50-100-fold. Analysis of the more amenable cleavage of BNPP revealed that the rate of BNPP cleavage is among the highest measured for mononuclear copper(II) complexes and is slightly higher than that reported for the close analogue [Cu(iPr3tacn)(OH2)2]2+. Detailed analysis required the determination of the pKa for [Cu(Me3tacn)(OH2)2]2+ and the constant for the dimerization of the conjugate base to [(Me3tacn)Cu(OH)2Cu(Me3tacn)]2+ (Kdim). Thermodynamic parameters derived from spectrophotometric pH titration and the analysis of the kinetic data were in reasonable agreement. Second-order rate constants for cleavage of BNPP by [Cu(Me3tacn)(OH2)(OH)]+ and associated activation parameters were obtained from initial rate analysis (k = 0.065 M(-1) s(-1) at 50.0 degrees C, deltaH = 56+/-6 kJ mol(-1), deltaS = -95+/-18 J K(-1) mol(-1)) and biphasic kinetic analysis (k = 0.14 M(-1) s(-1) at 50.0 degrees C, deltaH = 55+/-6 kJ mol(-1), deltaS = -92+/-20 J K(-1) mol(-1)). The negative entropy of activation is consistent with a concerted mechanism with considerable associative character. The complex was found to catalyze the cleavage of BNPP with turnover rates of up to 1 per day. Although these turnover rates can be considered low from an application point of view, the ability of the complexes to catalyze phosphate ester cleavage is clearly demonstrated.     

Coordination chemistry of a new cofacial binucleating macropolycycle derived from 1,4,7-triazacyclononane

We have prepared and characterized a new phenol-based compartmental ligand (H(2)L) incorporating 1,4,7-triazacyclononane ([9]aneN(3)), and we have investigated its coordination behavior with Cu(II), Zn(II), Cd(II), and Pb(II). The protonation constants of the ligand and the thermodynamic stabilities of the 1:1 and 2:1 (metal/ligand) complexes with these metal ions have been investigated by means of potentiometric measurements in aqueous solutions. The mononuclear [M(L)] complexes show remarkably high stability suggesting that, along with the large number of nitrogen donors available for metal binding, deprotonated phenolic functions are also involved in binding the metal ion. The mononuclear complexes [M(L)] show a marked tendency to add a second metal ion to afford binuclear species. The formation of complexes [M(2)(H(2)L)](4+) occurs at neutral or slightly acidic pH and is generally followed by metal-assisted deprotonation of the phenolic groups to give [M(2)(HL)](3+) and [M(2)(L)](2+) in weakly basic solutions. The complexation properties of H(2)L have also been investigated in the solid state. Crystals suitable for X-ray structural analysis were obtained for the binuclear complexes [Cu(2)(L)](BF(4))(2).(1)/(2)MeCN (1), [Zn(2)(HL)](ClO(4))(3).(1)/(2)MeCN (2), and [Pb(2)(L)](ClO(4))(2).2MeCN (4). In 1 and 2, the phenolate O-donors do not bridge the two metal centers, which are, therefore, segregated each within an N(5)O-donor compartment. However, in the case of the binuclear complex [Pb(2)(L)](ClO(4))(2).2MeCN (4), the two Pb(II) centers are bridged by the phenolate oxygen atoms with each metal ion sited within an N(5)O(2)-donor compartment of L(2)(-), with a Pb.Pb distance of 3.9427(5) A.     

Structural,spectroscopic, and electrochemical studies of binuclear manganese(II) complexes of bis(pentadentate) ligands derived from bis(1,4,7-triazacyclononane) macrocycles

Structural, electrochemical, ESR, and H2O2 reactivity studies are reported for [Mn(dmptacn)Cl]ClO4 (1, dmptacn = 1,4-bis(2-pyridylmethyl)-1,4,7-triazacyclononane) and binuclear complexes of bis(pentadentate) ligands, generated by attaching 2-pyridylmethyl arms to each secondary nitrogen in bis(1,4,7-triazacyclononane) macrocycles and linked by ethyl (tmpdtne, [Mn2(tmpdtne)Cl2](ClO4)2.2DMF, 2), propyl (tmpdtnp, [Mn2(tmpdtnp)Cl2](ClO4)2.3H2O, 3), butyl (tmpdtnb, [Mn2(tmpdtnb)Cl2](ClO4)2.DMF.2H2O, 4), m-xylyl (tmpdtn-m-X, [Mn2(tmpdtn-m-X)-Cl2](ClO4)2, 5) and 2-propanol (tmpdtnp-OH, [Mn2(tmpdtnp-OH)Cl2](ClO4)2, 6) groups. 1 crystallizes in the orthorhombic space group P2(1)2(1)2(1) (No. 19) with a = 7.959(7) A, b = 12.30(1) A, and c = 21.72(2) A; 2, in the monoclinic space group P2(1)/c (No. 14) with a = 11.455(4) A, b = 15.037(6) A, c = 15.887(4) A, and beta = 96.48(2) degrees; 3, in the monoclinic space group P2(1)/c (No. 14) with a = 13.334(2) A, b = 19.926(2) A, c = 18.799(1) A, and beta = 104.328(8) degrees; and [Mn2(tmpdtnb)Cl2](ClO4)2.4DMF.3H2O (4'), in the monoclinic space group P2(1)/n (No. 14) with a = 13.361(3) A, b = 16.807(5) A, c = 14.339(4) A, and beta = 111.14(2) degrees. Significant distortion of the Mn(II) geometry is evident from the angle subtended by the five-membered chelate (ca. 75 degrees) and the angles spanned by trans donor atoms (< 160 degrees). The Mn geometry is intermediate between octahedral and trigonal prismatic, and for complexes 2-4, there is a systematic increase in M...M distance with the length of the alkyl chain. Cyclic and square-wave voltammetric studies indicate that 1 undergoes a 1e- oxidation from Mn(II) to Mn(III) followed by a further oxidation to MnIV at a significantly more positive potential. The binuclear Mn(II) complexes 2-5 are oxidized to the Mn(III) state in two unresolved 1e- processes [MnII2-->MnIIMnIII-->MnIII2] and then to the MnIV state [MnIII2-->MnIIIMnIV-->MnIV2]. For 2, the second oxidation process was partially resolved into two 1e- oxidation processes under the conditions of square-wave voltammetry. In the case of 6, initial oxidation to the MnIII2 state occurs in two overlapping 1e- processes as was found for 2-5, but this complex then undergoes two further clearly separated 1e- oxidation processes to the MnIIIMnIV state at +0.89 V and the MnIV2 state at +1.33 V (vs Fc/Fc+). This behavior is attributed to formation of an alkoxo-bridged complex. Complexes 1-6 were found to catalyze the disproportionation of H2O2. Addition of H2O2 to 2 generated an oxo-bridged mixed-valent MnIIIMnIV intermediate with a characteristic 16-line ESR signal.     

Phosphodiester cleavage properties of copper(II) complexes of 1,4,7-triazacyclononane ligands bearing single alkyl guanidine pendants

Three new metal-coordinating ligands, L(1)·4HCl [1-(2-guanidinoethyl)-1,4,7-triazacyclononane tetrahydrochloride], L(2)·4HCl [1-(3-guanidinopropyl)-1,4,7-triazacyclononane tetrahydrochloride], and L(3)·4HCl [1-(4-guanidinobutyl)-1,4,7-triazacyclononane tetrahydrochloride], have been prepared via the selective N-functionalization of 1,4,7-triazacyclononane (tacn) with ethylguanidine, propylguanidine, and butylguanidine pendants, respectively. Reaction of L(1)·4HCl with Cu(ClO(4))(2)·6H(2)O in basic aqueous solution led to the crystallization of a monohydroxo-bridged binuclear copper(II) complex, [Cu(2)L(1)(2)(μ-OH)](ClO(4))(3)·H(2)O (C1), while for L(2) and L(3), mononuclear complexes of composition [Cu(L(2)H)Cl(2)]Cl·(MeOH)(0.5)·(H(2)O)(0.5) (C2) and [Cu(L(3)H)Cl(2)]Cl·(DMF)(0.5)·(H(2)O)(0.5) (C3) were crystallized from methanol and DMF solutions, respectively. X-ray crystallography revealed that in addition to a tacn ring from L(1) ligand, each copper(II) center in C1 is coordinated to a neutral guanidine pendant. In contrast, the guanidinium pendants in C2 and C3 are protonated and extend away from the Cu(II)-tacn units. Complex C1 features a single μ-hydroxo bridge between the two copper(II) centers, which mediates strong antiferromagnetic coupling between the metal centers. Complexes C2 and C3 cleave two model phosphodiesters, bis(p-nitrophenyl)phosphate (BNPP) and 2-hydroxypropyl-p-nitrophenylphosphate (HPNPP), more rapidly than C1, which displays similar reactivity to [Cu(tacn)(OH(2))(2)](2+). All three complexes cleave supercoiled plasmid DNA (pBR 322) at significantly faster rates than the corresponding bis(alkylguanidine) complexes and [Cu(tacn)(OH(2))(2)](2+). The high DNA cleavage rate for C1 {k(obs) = 1.30 (±0.01) × 10(-4) s(-1) vs 1.23 (±0.37) × 10(-5) s(-1) for [Cu(tacn)(OH(2))(2)](2+) and 1.58 (±0.05) × 10(-5) s(-1) for the corresponding bis(ethylguanidine) analogue} indicates that the coordinated guanidine group in C1 may be displaced to allow for substrate binding/activation. Comparison of the phosphate ester cleavage properties of complexes C1-C3 with those of related complexes suggests some degree of cooperativity between the Cu(II) centers and the guanidinium groups.     

Complexation of metal ions with TRAP (1,4,7-triazacyclononane phosphinic acid) ligands and 1,4,7-triazacyclononane-1,4,7-triacetic acid: phosphinate-containing ligands as unique chelators for trivalent gallium

Three phosphinic acid 1,4,7-triazacyclononane (TACN) derivatives bearing methylphosphinic (TRAP-H), methyl(phenyl)phosphinic (TRAP-Ph), or methyl(hydroxymethyl)phosphinic acid (TRAP-OH) pendant arms were investigated as members of a new family of efficient Ga(3+) chelators, TRAP ligands (triazacyclononane phosphinic acids). Stepwise protonation constants of ligands and stability constants of their complexes with Ga(3+), selected divalent metal, and Ln(3+) ions were determined by potentiometry. For comparison, equilibrium data for the metal ion-NOTA (1,4,7-triazacyclononane-1,4,7-triacetic acid) systems were redetermined. These ligands exhibit high thermodynamic selectivity for Ga(3+) over the other metal ions (log K(GaL) - log K(ML) = 7-9) and a selective complexation of smaller Mg(2+) over Ca(2+). Stabilities of the Ga(3+) complexes are dependent on the basicity of the donor atoms: [Ga(NOTA)] (log K(GaL) = 29.6) > [Ga(TRAP-OH)] (log K(GaL) = 23.3) > [Ga(TRAP-H)] (log K(GaL) = 21.9). The [Ga(TRAP-OH)] complex exhibits unusual reversible rearrangement of the "in-cage" N(3)O(3) complex to the "out-of-cage" O(6) complex. The in-cage complex is present in acidic solutions, and at neutral pH, Ga(3+) ion binds hydroxide anion, induces deprotonation and coordination of the P-hydroxymethyl group(s), and moves out of the macrocyclic cavity; the hypothesis is supported by a combination of results from potentiometry, multinuclear nuclear magnetic resonance spectrometry, and density functional theory calculations. Isomerism of the phosphinate Ga(3+) complexes caused by a combination of the chelate ring conformation, the helicity of coordinated pendant arms, and the chirality of the coordinated phosphinate groups was observed. All Ga(3+) complexes are kinetically inert in both acidic and alkaline solutions. Complex formation studies in acidic solutions indicate that Ga(3+) complexes of the phosphinate ligands are formed quickly (minutes) and quantitatively even at pH <2. Compared to common Ga(3+) chelators (e.g., 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) derivatives), these novel ligands show fast complexation of Ga(3+) over a broad pH range. The discussed TRAP ligands are suitable alternatives for the development of (68)Ga radiopharmaceuticals.     

Encapsulation of metal cations and anions within the cavity of bis(1,4,7-triazacyclononane) receptors

The synthesis and characterisation of a new bis([9]aneN3) ligand (L4) containing two [9]aneN3 macrocyclic moieties separated by a 2,6-dimethylenepyridine unit is reported. A potentiometric and 1H NMR study in aqueous solution reveals that ligand protonation occurs on the secondary amine groups and does not involve the pyridine nitrogen. The coordination properties toward Cu(II), Zn(II), Cd(II) and Pb(II) were studied by means of potentiometric and UV spectrophotometric measurements. The ligand can form mono- and binuclear complexes in aqueous solution. In the 1 : 1 complexes, the metal is sandwiched between the two [9]aneN3 moieties and the pyridine N-donor is coordinated to the metal, as actually shown by the crystal structure of the compound [ZnL4](NO3)2.CH3NO2. L4 shows a higher binding ability for Cd(II) with respect to Zn(II), probably due to a better fitting of Cd(II) ion inside the cavity generated by the two facing [9]aneN3 units. The formation of binuclear complexes is accompanied by the assembly of OH-bridged M2(OH)x (x = 1-3) clusters inside the cavity defined by the two facing [9]aneN3 units, and pyridine is not involved in metal coordination. A potentiometric and (1)H NMR study on the coordination of halogenide anions by L4 and its structural analogous L3 in which the two [9]aneN3 units are separated by a shorter quinoxaline linkage, shows that bromide is selectively recognised by L4, while chloride is selectively bound by L3. Such a behaviour is discussed in terms of dimensional matching between the spherical anions and the cavities generated by the two [9]aneN3 units of the receptors.     

Syntheses,structures and hydrolytic properties of copper(II) complexes of asymmetrically N-functionalised 1,4,7-triazacyclononane ligands

A series of new asymmetrically N-substituted derivatives of the 1,4,7-triazacyclononane (tacn) macrocycle have been prepared from the common precursor 1,4,7-triazatricyclo[5.2.1.0^4,10]decane: 1-ethyl-4-isopropyl-1,4,7-triazacyclononane (L1), 1-isopropyl-4-propyl-1,4,7-triazacyclononane (L2), 1-(3-aminopropyl)-4-benzyl-7-isopropyl-1,4,7-triazacyclononane (L3), 1-benzyl-4-isopropyl-1,4,7-triazacyclononane (L4) and 1,4-bis(3-aminopropyl)-7-isopropyl-1,4,7-triazacyclononane (L5). The corresponding monomeric copper(II) complexes were synthesised and were found to be of composition: [Cu(L1)Cl₂] · 1/2 H₂O (C1), [Cu(L4)Cl₂] · 4H₂O (C2), [Cu(L3)(MeCN)](ClO₄)₂ (C3), [Cu(L5)](ClO₄)₂ · MeCN · NaClO₄ (C4) and [Cu(L2)Cl₂] · 1/2 H₂O (C5). The X-ray crystal structures of each complex revealed a distorted square-pyramidal copper(II) geometry, with the nitrogen donors on the ligands occupying 3 (C1 and C2), 4 (C3) or 5 (C4) coordination sites on the Cu(II) centre. The metal complexes were tested for the ability to hydrolytically cleave phosphate esters at near physiological conditions, using the model phosphodiester, bis(p-nitrophenyl)phosphate (BNPP). The observed rate constants for BNPP cleavage followed the order k_C1 ≈ k_C2 > k_C5 ? k_C3 > k_C4, confirming that tacn-type Cu(II) complexes efficiently accelerate phosphate ester hydrolysis by being able to bind phosphate esters and also form the nucleophile necessary to carry out intramolecular cleavage. Complexes C1 and C2, featuring asymmetrically disubstituted ligands, exhibited rate constants of the same order of magnitude as those reported for the Cu(II) complexes of symmetrically tri-N-alkylated tacn ligands (k ∼ 1.5 × 10⁻⁵ s⁻¹).     

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…     

Coordination chemistry of a novel tetramacrocyclic ligand derived from 1,4,7-triazacyclononane: synthesis,structure, and properties of nickel(II) and copper(II) complexes

A new polynucleating ligand, 1,2,4,5-tetrakis(1,4,7-triazacyclonon-1-ylmethyl)benzene (Ldur), has been prepared and characterized as its dodecahydrobromide salt. Addition of base to an aqueous solution of this salt and 4 molar equivalents (m.e.) of a Ni(II) salt produces a mixture of bi- and trinuclear complexes, which can be separated by cation-exchange chromatography (CEC) and crystallized as [Ni2Ldur](ClO4)(4).2H2O (1) and [Ni3Ldur(H2O)6](ClO4)(6).9H2O (2). The "full capacity" tetranuclear complex, [Ni4Ldur(H2O)12](ClO4)(8).8H2O (3), is obtained by slow addition of Ldur to a refluxing aqueous solution of excess Ni2+ ions, followed by CEC purification. Treatment of Ldur with 4 m.e. of a copper(II) salt produces exclusively the tetranuclear complex, [Cu4Ldur(H2O)8](ClO4)(8).9H2O (4), while reaction with only 2 m.e. of Cu2+ ions yields the binuclear complex, [Cu2Ldur](ClO4)(4).4H2O (5). The X-ray structures of complexes 1,2,4, and [Cu2Ldur](ClO4)(4).3H2O (5') have been determined; all are monoclinic, P2(1)/c: for 1, a = 9.497(3) A, b = 13.665(5) A, c = 19.355(6) A, beta = 100.57(2) degrees, V = 2469(1) A3, and Z = 2; for 2, a = 22.883(7) A, b = 15.131(6) A, c = 20.298(8) A, beta = 97.20(3) degrees, V = 6973(4) A3, and Z = 4; for 4, a = 16.713(7) A, b = 16.714(6) A, c = 14.775(11) A, beta = 108.24(5) degrees, V = 3920(4) A3, and Z = 2; and for 5', a = 9.5705(1) A, b = 13.0646(1) A, c = 20.1298(2) A, beta = 103.1618(8) degrees, V = 2450.81(4) A3, and Z = 2. The metal centers in 1 and 5' lie in distorted octahedral environments, each facially coordinated by two of the triamine rings of Ldur, the cation in each case being centrosymmetric. In 2, one of the nickel(II) centers is similarly sandwiched by two triamine rings, while the other two nickel(II) centers are each coordinated by a single triamine ring from the ligand, with their distorted octahedral coordination spheres each being completed by three water molecules. In 4, the four triamine rings of Ldur bind to separate copper(II) centers, with two water molecules occupying the remaining two sites of the distorted square pyramidal (SP) coordination spheres, the cation again being centrosymmetric.     

Preparation of a new metallomicelle catalyst for the hydrolysis of bis(4-nitrophenyl) phosphate

A new metallomicellar system containing cerium(III), a macrocylic polyamine ligand, and the nonionic surfactant Brij35(polyoxyethylene(23) lauryl ether) was prepared and used as a catalyst in the hydrolysis of bis(4-nitrophenyl) phosphate (BNPP). Catalytic rate of the BNPP hydrolysis was measured kinetically using the UV-VIS spectrophotometric method. The results indicate that the metallomicellar system has relatively high stability and excellent catalytic function in the BNPP hydrolysis; also, the reaction rate of the BNPP catalytic hydrolysis increased by a factor of ca. 1 × 10¹⁰ compared to the BNPP spontaneous hydrolysis due to the catalytic effect of the active species and the local concentration effect of the micelles in the metallomicellar system. Experimental results also showed that the mono-hydroxy complex containing the macrocyclic polyamine ligand and cerium(III) is the real active species in the BNPP catalytic hydrolysis, and that the micelles provide a useful catalytic environment for the reaction. On basis of the research results, the reaction mechanism of BNPP catalytic hydrolysis has been proposed.     

A copper(II) complex of 1,4,7-triazacyclononane featuring acetate pendant: an efficient DNA cleavage agent

A new water-soluble copper(II) complex, Cu(TACNA)Br?·?0.375H₂O (1) [TACNA?=?1,4,7-triazacyclononane-N-acetate], has been synthesized to serve as artificial nucleases. The X-ray crystal structure of 1 indicates that one bromide and an oxygen from acetate pendant coordinate to copper(II) in addition to the nitrogen atoms in the TACN macrocycle, resulting in a five-coordinate complex with square-pyramidal geometry. The interaction of 1 with calf thymus DNA (ct-DNA) has been investigated by UV absorption and fluorescence spectroscopies, and the mode of ct-DNA binding for 1 has been proposed. In the absence of external agents, supercoiled plasmid DNA cleavage by 1 was performed under aerobic condition; the influences on DNA cleavage of different complex concentrations and reaction times were also studied. The cleavage of plasmid DNA likely involves oxidative mechanism.     

Efficient plasmid DNA cleavage by copper(II) complexes of 1,4,7-triazacyclononane ligands featuring xylyl-linked guanidinium groups

Three new metal-coordinating ligands, L(1), L(2), and L(3), have been prepared by appending o-, m-, and p-xylylguanidine pendants, respectively, to one of the nitrogen atoms of 1,4,7-triazacyclononane (tacn). The copper(II) complexes of these ligands are able to accelerate cleavage of the P-O bonds within the model phosphodiesters bis(p-nitrophenyl)phosphate (BNPP) and [2-(hydroxypropyl)-p-nitrophenyl]phosphate (HPNPP), as well as supercoiled pBR 322 plasmid DNA. Their reactivity toward BNPP and HPNPP is not significantly different from that of the nonguanidinylated analogues, [Cu(tacn)(OH(2))(2)](2+) and [Cu(1-benzyl-tacn)(OH(2))(2)](2+), but they cleave plasmid DNA at considerably faster rates than either of these two complexes. The complex of L(1), [Cu(L(1)H(+))(OH(2))(2)](3+), is the most active of the series, cleaving the supercoiled plasmid DNA (form I) to the relaxed circular form (form II) with a k(obs) value of (2.7 ± 0.3) × 10(-4) s(-1), which corresponds to a rate enhancement of 22- and 12-fold compared to those of [Cu(tacn)(OH(2))(2)](2+) and [Cu(1-benzyl-tacn)(OH(2))(2)](2+), respectively. Because of the relatively fast rate of plasmid DNA cleavage, an observed rate constant of (1.2 ± 0.5) × 10(-5) s(-1) for cleavage of form II DNA to form III was also able to be determined. The X-ray crystal structures of the copper(II) complexes of L(1) and L(3) show that the distorted square-pyramidal copper(II) coordination sphere is occupied by three nitrogen atoms from the tacn ring and two chloride ions. In both complexes, the protonated guanidinium pendants extend away from the metal and form hydrogen bonds with solvent molecules and counterions present in the crystal lattice. In the complex of L(1), the distance between the guanidinium group and the copper(II) center is similar to that separating the adjacent phosphodiester groups in DNA (ca. 6 ?). The overall geometry of the complex is also such that if the guanidinium group were to form charge-assisted hydrogen-bonding interactions with a phosphodiester group, a metal-bound hydroxide would be well-positioned to affect the nucleophilic attack on the neighboring phosphodiester linkage. The enhanced reactivity of the complex of L(1) at neutral pH appears to also be, in part, due to the relatively low pK(a) of 6.4 for one of the coordinated water molecules.     

Syntheses,structures, and spectroscopic properties of copper(II) and cobalt(III) complexes containing 1,4,7-tribenzyl-1,4,7-triazacyclononane ligand

Three new complexes [CuL(N₃)₂] (1), [CuL(SCN)₂] (2), and [CoL(SCN)₃] (3) (L?=?1,4,7-tribenzyl-1,4,7-triazacyclononane) have been synthesized and structurally characterized. Complex 1 crystallizes in monoclinic space group P2(1)/n with unit cell parameters a?=?14.105(7), b?=?8.999(5), c?=?21.603(11)?Å, β?=?100.470(7)°. While 2 crystallizes in triclinic space group P-1 with unit cell parameters a?=?9.6380(16), b?=?10.6993(18), c?=?15.798(3)?Å, α?=?106.636(3), γ?=?116.478(3)°. Complex 3 crystallizes in trigonal space group P–3c1 with unit cell parameters a?=?14.744(3), b?=?14.744(3), c?=?16.098(4)?Å, γ?=?120°. Elemental analysis, IR, UV-vis spectra of complexes 1–3 and ESR spectra of complexes 1–2 were also determined.     

Lanthanide complexes of new nonadentate imino-phosphonate ligands derived from 1,4,7-triazacyclononane: synthesis, structural characterisation and NMR studies

The polyamino ligand 1,4,7-tris(2-aminoethyl)-1,4,7-triazacyclononane (1) has been used to synthesise two new ligands by Schiff-base condensation with methyl sodium acetyl phosphonate to give ligand L and methyl sodium 4-methoxybenzoyl phosphonate to give ligand L1 in the presence of lanthanide ion as templating agent to form the complexes [Ln(L)] and [Ln(L1)](Ln = Y, La, Gd, Yb). Both ligands L and L1 have nine donor atoms comprising three amine and three imine N-donors and three phosphonate O-donors and form Ln(III) complexes in which the three pendant arms of the ligands wrap around the nine-coordinate Ln(III) centres. Complexes with Y(III), La(III), Gd(III) and Yb(III) have been synthesised and the complexes [Y(L)], [Gd(L)] and [Gd(L1)] have been structurally characterised. In all the complexes the coordination polyhedron about the lanthanide centre is slightly distorted tricapped trigonal prismatic with the two triangular faces of the prism formed by the macrocyclic N-donors and the phosphonate O-donors. Interestingly, given the three chiral phosphorus centres present in [Ln(L)] and [Ln(L1)] complexes, the three crystal structures reported show the presence of only one diastereomer of the four possible. 1H, 13C and 31P NMR spectroscopic studies on diamagnetic [Y(L)] and [La(L)] and on paramagnetic [Yb(L)] complexes indicate the presence in solution of all the four different diastereomers in varying proportions. The stability of complexes [Y(L)] and [Y(L1)] in D2O in both neutral and acidic media, and the relaxivity of the Gd(III) complexes, have also been investigated.     

Tmtacn, tacn, and triammine complexes of (eta 6-arene)OsII: syntheses, characterizations, and photosubstitution reactions (tmtacn = 1,4,7-trimethyl-1,4,7-triazacyclononane; tacn = 1,4,7-triazacyclononane)

A series of (eta 6-arene)OsII complexes containing the saturated nitrogen donor ligands tmtacn, tacn, and NH3 are prepared and characterized. The electrochemical properties and photochemical reactions of these complexes are studied, and the solid-state structures for [(eta 6-p-cymene)Os(tacn)](PF6)2 (1) and [(eta 6-p-cymene)Os(tmtacn)](PF6)2 (2) are determined. Single-crystal X-ray data: 1, orthorhombic, space group Pbca-D2h15 (No. 61), with a = 14.716(3) A, b = 17.844(3) A, c = 18.350(4) A, V = 4819(2) A3, and Z = 8; 2, monoclinic, space group C2-C2(3) (No. 5), with a = 17.322(4) A, b = 10.481(3) A, c = 15.049(4) A, beta = 98.72 degrees, V = 2701(1) A3, and Z = 4.