Distribution by Scientific Domains
Distribution within Chemistry

Selected Abstracts

Structure and conformation of a nickel complex: {2-Hydroxo-3-piperidine-1-yl-methyl-N,N,(bis-5-bromobenzylpropylenediimine)nickel(II)perchlorate}

S. M. Malathy Sony
Abstract The title compound, a nickel complex [C23H26N3O2Br2Ni.(ClO4)] (CCDC 199520) crystallizes in triclinic space group P with the cell parameters a = 10.2560(4), b = 10.8231(4), c = 12.0888(5)Å, , = 99.404(1), , = 99.780(1), , = 92.252(1)° and V = 1301.49(9)Å3. The structure was solved by Patterson method and refined by full-matrix least-squares procedures to a final R = 0.0497 using 6287 observed reflections. In the complex, the piperidine ring takes chair conformation and the geometry around the Ni ion is slightly distorted square planar. The dihedral angle between the planes [N-Ni-N and O-Ni-O] is 9.4(1)°. The chelate ring containing both the nitrogen atoms adopts twisted boat conformation. The molecules in the crystal are stabilized by N-H,O and C-H,O types of hydrogen bonds in addition to a C-H,, interaction. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source]

Aluminum(III) Porphyrins as Ionophores for Fluoride Selective Polymeric Membrane Electrodes

Abstract Aluminum(III) porphyrins are examined as potential fluoride selective ionophores in polymeric membrane type ion-selective electrodes. Membranes formulated with Al(III) tetraphenyl (TPP) or octaethyl (OEP) porphyrins are shown to exhibit enhanced potentiometric selectivity for fluoride over more lipophilic anions, including perchlorate and thiocyanate. However, such membrane electrodes display undesirable super-Nernstian behavior, with concomitant slow response and recovery times. By employing a sterically hindered Al(III) picket fence porphyrin (PFP) complex as the membrane active species, fully reversible and Nernstian response toward fluoride is achieved. This finding suggests that the super-Nernstian behavior observed with the nonpicket fence metalloporphyrins is due to the formation of aggregate porphyrin species (likely dimers) within the membrane phase. The steric hindrance of the PFP ligand structure eliminates such chemistry, thus leading to theoretical response slopes toward fluoride. Addition of lipophilic anionic sites into the organic membranes enhances response and selectivity, indicating that the Al(III) porphyrin ionophores function as charged carrier type ionophores. Optimized membranes formulated with Al(III)-PFP in an o -nitrophenyloctyl ether plasticized PVC film exhibit fast response to fluoride down to 40,,M, with very high selectivity over SCN,, ClO4,, Cl,, Br, and NO3, (kpot<10,3 for all anions tested). With further refinements in the membrane chemistry, it is anticipated that Al(III) porphyrin-based membrane electrodes can exhibit potentiometric fluoride response and selectivity that approaches that of the classical solid-state LaF3 crystal-based fluoride sensor. [source]

Application of dodecyldimethyl (2-hydroxy-3-sulfopropyl) ammonium in wall modification for capillary electrophoresis separation of proteins

Wei Wei
Abstract A zwitterionic surfactant, dodecyldimethyl (2-hydroxy-3-sulfopropyl) ammonium (C12H25N+(CH3)2CH2CHOHCH2SO3,), named dodecyl sulfobetaine (DSB), was used as a novel modifier to coat dynamically capillary walls for capillary electrophoresis separation of basic proteins. The DSB coating suppressed the electroosmotic flow (EOF) in the pH range of 3,12. At high DSB concentration, the EOF was suppressed by more than 8.8,times. The DSB coating also prevented successfully the adsorption of cationic proteins on the capillary wall. Anions, such as Cl,, Br,, I,, SO42,, CO32,, and ClO4,, could be used as running buffer modifiers to adjust the EOF for better separation of analytes. Using this dynamically coated capillary, a mixture of eight inorganic anions achieved complete separation within 4.2,min with the efficiencies from 24,000 to 1,310,000,plates/m. In the presence of ClO4, as EOF adjustor, the separation of a mixture containing four basic proteins (lysozyme, cytochrome c, ,-chymotrypsinogen,A, and myoglobin) yielded efficiencies of 204,000,896,000,plates/m and recoveries of 88%,98%. Migration time reproducibility of these proteins was less than 0.5% relative standard deviation (RSD) from run to run and less than 3.1% RSD from day to day, showing promising application of this novel modifier in protein separation. [source]

Magneto,Structural Correlations in Discrete MnII -WV Cyano-Bridged Assemblies with Polyimine Ligands

Robert Podgajny
Abstract We present the magneto,structural correlations for two novel discrete cyano-bridged assemblies based on cationic complexes of manganese(II) with diimine ligands and octacyanotungstate(V) ions. The crystal structure of [MnII(terpy)(dmf)(H2O)2][MnII(terpy)(H2O)(dmf)(,-NC)WV(CN)7]2·6H2O (1) (terpy = 2,2,;6,,2,-terpyridine, dmf = dimethylformamide) contains dinuclear {MnIIWV}, cyano-bridged anions, while the crystal structure of [MnII(phen)3]2[MnII(phen)2(,-NC)2WV(CN)6]2(ClO4)2·9H2O (2) (phen = 1,10-phenanthroline) is built of tetranuclear {MnII2WV2}2, square anions. Intramolecular Mn,W magnetic interactions through the cyano bridges are represented by magnetic coupling constants J = ,39 cm,1 for the {MnIIWV}, unit in 1 and J1 = ,25.7 and J2 = ,16.7 cm,1 for the {MnII2WV2}2, unit in 2. J and J1 represent relatively strong W,CN,Mn interactions and are ascribed to the bridges in b positions of TPRS-8 (trigonal prism square-face bicapped) of [W(CN)8]3, polyhedra, favoring the strongest electronic interactions between the d,d orbital of W and the ,* orbitals of CN,, whereas J2 is related to the m vertex of [W(CN)8]3,. The magnetic properties of 1 and 2 are compared with reference compounds and discussed in the context of the type of coordination polyhedra of [W(CN)8]3, as well as the metric parameters of cyano-bridged W,CN,Mn linkages. We found the type of coordination polyhedra and bridging mode of [W(CN)8]3, to be the most important factors influencing the magnitude of the Mn,W magnetic interaction. [source]

A ,3 -Alkoxo-Bridged Tetranuclear [Cu4L2] Copper(II) Complex of a Hexadentate N2O4 Donor Ligand with a [6 + 0] Cu4O4 Cubane Core: Synthesis, Crystal Structure, and Magnetic Properties

Dipankar Maity
Abstract A novel hexacoordinating non-Schiff base ligand (H4L) with N2O4 donor atoms has been synthesized by simple Mannich reactions. The use of this ligand with Cu(ClO4)2·6H2O in different molar ratios as well as pH leads to the formation of a mononuclear species and a tetranuclear CuII complex possessing a cubane [Cu4L2] core with almost equal Cu···Cu separation. In the presence of an excess amount of copper(II) ions and triethylamine at reflux, the mononuclear [CuH2L] species can be converted into the tetranuclear one, whereas the reverse process was not observed even after prolonged reaction time. Both the complexes have been characterized by single-crystal X-ray diffraction and magnetic measurements. Magnetic studies reveal that complex 1 displays a paramagnetic Curie-type behavior whereas 2 displays a singlet-spin ground state induced by strong intramolecular antiferromagnetic interactions. [source]

Syntheses, Structures and Magnetic Properties of Trinuclear CuIIMIICuII (M = Cu, Ni, Co and Fe) and Tetranuclear [2×1+1×2] CuIIMnII,2CuII Complexes Derived from a Compartmental Ligand: The Schiff Base 3-Methoxysalicylaldehyde Diamine Can also Stabilize a Cocrystal

Arpita Biswas
Abstract The present investigation describes syntheses, characterization and studies of the mononuclear compound [CuIIL,(H2O)] (1), the triangular, trinuclear monophenoxido-bridged compounds [{CuIIL}2MII(H2O)2](ClO4)2·nH2O [2 (M = Cu, n = 0), 3 (M = Ni, n = 3), 4 (M = Co, n = 0), 5 (M = Fe, n = 0)] and the tetrametallic self-assembled complex [{CuIILMnII(H2O)3}{CuIIL}2](ClO4)2·H2O (6) derived from compartmental Schiff base ligand, H2L, which is the [2+1] condensation product of 3-methoxysalicylaldehyde and trans -1,2-diaminocyclohexane. Single-crystal X-ray structures of 2, 5 and 6 were determined. Two pairs of terminal···central metal ions in the trinuclear cores in 2 and 5 are monophenoxido-bridged. Interestingly, the CuO6 and FeO6 environments have tetragonally compressed octahedral geometries. On the other hand, the structure of 6 reveals that it is a [2×1+1×2] cocrystal of one diphenoxido-bridged dinuclear [CuIILMnII(H2O)3]2+ dication and two mononuclear [CuIIL] moieties. Cocrystallization in 6 takes place as a result of water encapsulation. The variable-temperature (2,300 K) magnetic susceptibilities of compounds 2,6 have been measured. The exchange integrals obtained are: the CuII3 compound 2, J = ,78.9 cm,1; the CuIINiIICuII compound 3, J = ,22.8 cm,1; the CuIICoIICuII compound 4, J = ,7.8 cm,1; the CuIIFeIICuII compound 5, J = ,3.0 cm,1; the CuII3MnII compound 6, J = ,15.1 cm,1. The monophenoxido-bridging core in 3 and 4 has been proposed after comparison of the structures and magnetic properties of these two compounds with those of 2, 5 and related other compounds. This paper presents rare examples of monophenoxido-bridged CuIIMIICuII (M = Cu, Ni, Co and Fe) compounds, provides an understanding of the structures from magnetic exchange integrals, and, most importantly, reports on the first example of a cocrystal derived from a 3-methoxysalicylaldehyde diamine compartmental ligand. [source]

Dehydrogenation of Hydridoirida-,-diketones in Methanol: The Selective Formation of Mono- and Dinuclear Acyl Complexes

Roberto Ciganda
Abstract The hydridoirida-,-diketone [IrH{(PPh2(o -C6H4CO))2H}Cl] (1) reacts with diimines (NN) or with pyridine (py) in refluxing methanol to undergo dehydrogenation. The reactions afford selectively the cis -acyl, trans -phosphane isomers of the cationic [Ir(PPh2(o -C6H4CO))2(NN)]+ {NN = 2,2,-bipyridine (2); R,N=C(CH3),C(CH3)=N,R, [R = R, = NH2 (3); R = R, = OH (4); R = OH, R, = NH2 (5)]} or neutral [IrCl(PPh2(o -C6H4CO))2(py)] (6) derivatives. The reactions are faster for ligands containing amino substituents. Refluxing 1 in MeOH affords the formation of an equimolar mixture of dimercationic species [Ir2(,-Cl)(,-PPh2(o -C6H4CO))2(PPh2(o -C6H4CO))2]+ (7a and 7b) containing two acyls and a chloride as bridging groups. The isomers could be separated by fractional precipitation. Compound [3]Cl, containing amino substituents in the imino functionalities, catalyses the hydrogen transfer from 2-propanol to cyclohexanone to afford cyclohexanol. All the complexes were fully characterised spectroscopically. Single crystal X-ray diffraction analysis was performed on complexes 6 and [7b]ClO4. [source]

Structural, Spectroscopic, and Proton-Coupled Electron-transfer Behavior of Pyrazolyl-3,5-bis(benzimidazole)-Bridged Homo- and Heterochiral RuIIRuII, OsIIOsII, and OsIIRuII 2,2,-Bipyridine Complexes

Sujoy Baitalik
Abstract The homo- and heterobimetallic complexes [(bpy)2MII(H2pzbzim)M,II(bpy)2](ClO4)3·nH2O (1, 3, 5) and their corresponding deprotonated complexes [(bpy)2MII(pzbzim)M,II(bpy)2](ClO4)·nH2O (2, 4, 6) [where MII, M,II = Ru (1, 2) = Os (3, 4); MII = Os and M,II = Ru (3, 5); bpy = 2,2,-bipyridine; H3pzbzim = pyrazole-3,5-bis(benzimidazole)] were synthesized, separated to their heterochiral (a, ,,/,,) and homochiral (b, ,,/,,) diastereoisomers, and characterized by elemental analyses, ESI-MS, and 1H NMR spectroscopy. The X-ray structures of 1a, 3a, and 5a show the involvement of two pyridine rings of two bpy ligands in strong intramolecular nonbonded ,,, interaction. The occurrence of a C,H···, interaction between an aromatic C,H and the ,-cloud of a pyridine ring leads to strong electronic shielding of this proton (1H NMR). In all cases, the two diastereoisomers show practically no differences in their absorption spectra, redox potentials, and pK values. The large shifts in the E1/2 values to less positive potentials and substantial redshifts in the MLCT bands that occur on deprotonation of 1, 3, and 5 are energetically correlated. From the profiles of E1/2(1), (2) vs. pH over the pH range 1,12, the equilibrium constants and standard redox potentials for all the complex species in the metal oxidation states II·II, II·III, and III·III and the bridged ligand in the protonation states H2pzbzim,, Hpzbzim2,, and pzbzim3, have been evaluated. Using these values the bond dissociation free energies for the benzimidazole N,H bonds have been estimated. Spectroelectrochemical studies have been carried out for 1a, 3a, and 5a in the range 400,1100 nm. With stepwise oxidation of the metal centers replacement of MLCT bands by LMCT bands occur gradually with the observation of sharp isosbestic points. In the case of 1a, a band observed at ,max = 910 nm for the RuIIRuIII species has been ascribed to intervalence charge transfer (IVCT) transition. [source]

Nucleophilic Addition of Water and Alcohols to Dicyanonitrosomethanide: Ligands with Diverse Bonding Modes in Magnetically Coupled d-Block Complexes

Anthony S. R. Chesman
Abstract Ligands resulting from the transition-metal-promoted nucleophilic addition of water or an alcohol to dicyanonitrosomethanide ions (dcnm) have been utilised in the formation of a large series of polynuclear complexes. Addition of water to dcnm results in formation of carbamoylcyanonitrosomethanide (ccnm); deprotonation of this ligand gives amidocarbonyl(cyano)nitrosomethanide (acnm), which has been incorporated into the trinuclear complex [Cu3(acnm)2(dmae)2(H2O)2] [dmae = 2-(dimethylamino)ethoxide] (1) which shows strong antiferromagnetic coupling with an exchange coupling constant, J = ,500 cm,1. [Cu(acnm)(NH3)2], (2) marks the first instance of acnm facilitating the formation of a coordination polymer, namely a 1D chain with intramolecular hydrogen bonding. Attempts to synthesise 2 through different reaction conditions instead resulted in the mononuclear [Cu(acnm)(NH3)2(py)] (py = pyridine) (3). The addition of ethanol to dcnm results in cyano[imino(ethoxy)methyl]nitrosomethanide (cenm) which features in the mononuclear [Cu(cenm)2(H2O)2] (4) and polymeric {[Cu(cenm)2]2·H2O}, (5). The latter is the first example of the cenm ligand in a coordination polymer and has a highly unusual coordination mode through the nitrile groups and extremely weak antiferromagnetic coupling. {[Mn3(ccnm)2(EtOH)2(OAc)4]·2EtOH}, (6) and (Et4N)2[Cu(ccnm)4] (7) contain previously unobserved coordination modes of the ccnm ligand while the complex [Mn(cmnm)3Mn(bipy)(MeOH)](ClO4) (8) {cmnm = cyano[imino(methoxy)methyl]nitrosomethanide, bipy = 2,2,-bipyridine} displays weak antiferromagnetic coupling between manganese atoms with J = ,1.44 cm,1. A change in the solvent systems used in the synthesis of 7 results in the formation of the mononuclear complexes [Mn(bipy)2(dcnm)2] (9) or [Mn(bipy)2(H2O)(dcnm)](dcnm)·H2O (10) and [Mn(bipy)2(dcnm)(H2O)](dcnm) (11). The addition of ethlyene glycol monomethyl ether to dcnm gives cyano[imino(2-methoxyethoxy)methyl]nitrosomethanide (cgnm) and the formation of [Cu(cgnm)2(H2O)2] (12). [source]

Copper Complexes with Neutral N4 Tripodal Ligands: Influence of the Number of Nitrogen Donors on Their Structures, Properties, and Reactivity,

Kiyoshi Fujisawa
Abstract Copper coordination complexes of the neutral tetradentate nitrogen-containing ligands tris(3,5-dimethylpyrazol-1-ylmethyl)amine (L0N4) and tris(3,5-diisopropylpyrazol-1-ylmethyl)amine (L1N4), namely the copper(II) chlorido complexes [CuII(L0N4)Cl2] (1) and [CuII(L1N4)Cl2] (2), the copper(II) nitrato complexes [CuII(L0N4)(NO3)](NO3) (3) and [CuII(L1N4)(NO3)](NO3) (4), and the copper(II) sulfato complexes [CuII(L0N4)(SO4)] (5) and [CuII(L1N4)(SO4)] (6), and the copper(I) complexes [CuI(L0N4)](PF6) (7) and [CuI(L0N4)(PPh3)](ClO4) (8), have been systematically synthesized in order to investigate the influence of the number of nitrogen donors on their structures, properties, and reactivity. All copper(II) complexes were fully characterized by X-ray crystallography and by IR/far-IR, UV/Vis absorption, and ESR spectroscopy. Although the structure of 7 was not determined by X-ray crystallography, this complex and the structurally characterized copper(I) triphenylphosphane complex 8 were fully characterized by IR/far-IR and NMR spectroscopy. A comparison of the copper(II) complexes with two tris(pyrazol-1-ylmethyl)amine ligands with different bulkiness of the pyrazolyl rings has allowed us to evaluate the second coordination sphere effects of the ligands. Moreover, the structures and physicochemical properties of these complexes are compared with those of related complexes containing the neutral tridentate tris(pyrazolyl)methane ligand and the neutral bidentate bis(pyrazolyl)methane ligand. Finally, the relative stability of the copper(I) complexes is discussed. The influence of the number of nitrogen donors in copper complexes is observed from these systematic results.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]

Bis(terdentate) Pyrazole/Pyridine Ligands: Synthesis, Crystal Structures and Magnetic Properties of Bridged Binuclear and Tetranuclear Copper(II) Complexes

Akhilesh Kumar Singh
Abstract A new binucleating bis(terdentate) ligand, 3,5-[3-bis(2-pyridyl)pyrazole-1-ylmethyl]pyrazole (HL2), was synthesized. Reaction of the deprotonated ligand L2 with hydrated CuII salts gives (,-pyrazolato)(,-hydroxido)-bridged binuclear and tetranuclear complexes [L2Cu2(,-OH)(ClO4)(MeCN)](ClO4) (2), [L2Cu2(dmf)2(,3 -OH)]2(ClO4)4·4dmf (3·4dmf) and [L2L,Cu2](ClO4)2 [4; HL, = 3-(2-pyridyl)pyrazole]. In these complexes, both ,-OH and ,3 -OH bridges were observed. This contrasts the situation for a dicopper(II) complex of the related bis(terdentate) ligand 3,5-bis[6(2,2,-dipyridyl)]pyrazole (HL1), {L1Cu2(OMe)(MeOH)[,1 - O -(NO3)]}{[Cu2(NO3)2(,-OMe)2]}0.5·MeOH (1·MeOH), where the shorter and more rigid ligand side arms enforce a larger Cu···Cu separation and the formation of a MeO,HOMe moiety within the bimetallic pocket. Molecular structures of all complexes were elucidated by X-ray crystallography. Variable-temperature magnetic susceptibility measurements (295,2 K) for powdered samples of complexes 2,4 reveal strong antiferromagnetic coupling between two copper centres. The magnitude of the coupling is discussed in view of the structural features. During the preparation of complex 4, partial ligand hydrolysis was also observed, but this strongly depends on the reaction conditions.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]

One-Dimensional Coordination Polymers of MnII, CuII, and ZnII Supported by Carboxylate-Appended (2-Pyridyl)alkylamine Ligands , Structure and Magnetism

Himanshu Arora
Abstract Four new complexes [MnII(L1OO)(H2O)][ClO4]·2H2O (1), [ZnII(L1OO)][ClO4]·2H2O (2), [CuII(L3OO)][CF3SO3]·H2O (3), and [ZnII(L3OO)][ClO4] (4) (L1OO, = 3-[(2-(pyridine-2-yl)ethyl){2-(pyridine-2-yl)methyl}amino]propionate; L3OO, = 3-[(2-(pyridine-2-yl)ethyl){(dimethylamino)ethyl}amino]propionate) have been synthesized and characterized by elemental analysis, IR, and UV/Vis spectroscopy. Structural analysis revealed that 1, 3, and 4 are one-dimensional chain-like coordination polymers. In 1 distorted octahedral MnN3O3 and in 3 square-pyramidal CuN3O2 coordination is satisfied by three nitrogen atoms and an appended carboxylate oxygen atom of the ligand, and an oxygen atom belonging to the carboxylate group of an adjacent molecule. In 4 trigonal bipyramidal ZnN3O2 coordination environment is provided by two nitrogen atoms and an appended carboxylate oxygen atom of the ligand in the equatorial plane, and the two axial positions are satisfied by a tertiary amine nitrogen and an oxygen atom belonging to the carboxylate group of an adjacent molecule. In 1 the MnII center is coordinated by an additional water molecule. In these complexes each monomeric unit is sequentially connected by syn - anti carboxylate bridges. Temperature-dependent magnetic susceptibilities for 1 and 3 are measured, revealing antiferromagnetic interactions through syn - anti carboxylate bridges between the MII centers. Analysis of the crystal packing diagram reveals that in 1 extensive ,,, stacking involving alternate pyridine rings of adjacent 1D chain exists, which eventually lead to the formation of a 2D network structure. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]

Unconventional Spin Crossover in Dinuclear and Trinuclear Iron(III) Complexes with Cyanido and Metallacyanido Bridges

Abstract A nonsymmetrical triamine, 1,6-diamino-4-azahexane, was Schiff-condensed with (X-substituted) o -salicylaldehyde to yield pentadentate ligands X-L5: salpet and MeBu-salpet. These ligands form mononuclear, dinuclear, and trinuclear FeIII complexes, whose structures were determined by single-crystal X-ray analysis. Of the mononuclear complexes, [FeIII(salpet)Cl] and [FeIII(MeBu-salpet)Cl] are high spin (S = 5/2), whereas [FeIII(salpet)CN]·MeOH is low spin (S = 1/2). The dinuclear and trinuclear complexes show a kind ofthermally induced spin crossover. The dinuclear complex [L5FeIII(CN)FeIIIL5](ClO4)·2H2O (L5 = salpet) is a mixed-spin assembly: the C -coordinated FeIII center is low spin (L) and the N -coordinated FeIII center is high spin (H) at low temperature; an antiferromagnetic interaction occurs between them. This LH reference state is mixed with the LL one. Upon heating, the system shows an increasing content of the HH state. Also, the dinuclear complex [L5FeIII(CN)FeIIIL5](BPh4)·2MeCN (L5 = MeBu-salpet) exhibits a spin transition between LH and HH spin pairs. The mixed-valence trinuclear complex [L5FeIII{FeII(CN)5(NO)}FeIIIL5]·0.5MeOH·3.75H2O (L5 = salpet) shows spin crossover with a residual high-spin fraction at liquid He temperature owing to the LL + LH ground state. The metallacyanido-bridged complex [L5FeIII{Ni(CN)4}FeIIIL5]·2MeOH (L5 = MeBu-salpet) contains a high-spin pair, HH, over the whole temperature interval with a ferromagnetic exchange interaction. A theoretical model was outlined that allows simultaneous fitting of all available experimental data (magnetic susceptibility, magnetization, high-spin mole fraction obtained from the Mössbauer spectra) on a common set of parameters. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]

Anion-Directed Template Synthesis and Hydrolysis of Mono-Condensed Schiff Base of 1,3-Pentanediamine and o -Hydroxyacetophenone in NiII and CuII Complexes

Pampa Mukherjee
Abstract Bis(o -hydroxyacetophenone)nickel(II) dihydrate, on reaction with 1,3-pentanediamine, yields a bis-chelate complex [NiL2]·2H2O (1) of mono-condensed tridentate Schiff baseligand HL {2-[1-(3-aminopentylimino)ethyl]phenol}. The Schiff base has been freed from the complex by precipitating the NiII as a dimethylglyoximato complex. HL reacts smoothly with Ni(SCN)2·4H2O furnishing the complex [NiL(NCS)] (2) and with CuCl2·2H2O in the presence of NaN3 or NH4SCN producing [CuL(N3)]2 (3) or [CuL(NCS)] (4). On the other hand, upon reaction with Cu(ClO4)2·6H2O and Cu(NO3)2·3H2O, the Schiff base undergoes hydrolysis to yield ternary complexes [Cu(hap)(pn)(H2O)]ClO4 (5) and [Cu(hap)(pn)(H2O)]NO3 (6), respectively (Hhap = o -hydroxyacetophenone and pn = 1,3-pentanediamine). The ligand HL undergoes hydrolysis also on reaction with Ni(ClO4)2·6H2O or Ni(NO3)2·6H2O to yield [Ni(hap)2] (7). The structures of the complexes 2, 3, 5, 6, and 7 have been confirmed by single-crystal X-ray analysis. In complex 2, NiII possesses square-planar geometry, being coordinated by the tridentate mono-negative Schiff base, L and the isothiocyanate group. The coordination environment around CuII in complex 3 is very similar to that in complex 2 but here two units are joined together by end-on, axial-equatorial azide bridges to result in a dimer in which the geometry around CuII is square pyramidal. In both 5 and 6, the CuII atoms display the square-pyramidal environment; the equatorial sites being coordinated by the two amine groups of 1,3-pentanediamine and two oxygen atoms of o -hydroxyacetophenone. The axial site is coordinated by a water molecule. Complex 7 is a square-planar complex with the Ni atom bonded to four oxygen atoms from two hap moieties. The mononuclear units of 2 and dinuclear units of 3 are linked by strong hydrogen bonds to form a one-dimensional network. The mononuclear units of 5 and 6 are joined together to form a dimer by very strong hydrogen bonds through the coordinated water molecule. These dimers are further involved in hydrogen bonding with the respective counteranions to form 2-D net-like open frameworks. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source]

Guest-Inclusion Behavior of Double-Strand 1D Coordination Polymers Based on N,N, -Type Schiff Base Ligands

Qing Wang
Abstract Four double-strand one-dimensional (1D) coordinationpolymers, namely, {[Ni(N3Py)2(NO3)2]·(C6H6)x·C2H5OH}n (1), [Cd(ImBNN)2(CH3C6H4SO3)2]n (2), {[Co(N3OPy)2(H2O)2](ClO4)2·C6H6·H2O}n (3), and {[Co(N3OPy)2(H2O)2](ClO4)2·(C8H10)x}n (4) were obtained from the assembly of three N,N, -type Schiff base ligands, 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene (N3Py), 2,5-bis(4,-(imidazol-1-yl)benzyl)-3,4-diaza-2,4-hexadiene (ImBNN), and bis[4-(3-pyridylmethylenemino)phenoxy]methane (N3OPy), with transition-metal ions. All complexes were characterized by single-crystal X-ray diffraction, X-ray powder diffraction, and FTIR measurements. The guest-inclusion behavior of these complexes were investigated by thermogravimetric and X-ray powder diffraction analyses. The structural relationship between the ligands and the cavity sizes and packing fashions have been discussed to elucidate the distinctive guest-inclusion behavior of these complexes.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source]

Cobalt(III) Complexes of a Tripodal Ligand Containing Three Imidazole Groups: Properties and Structures of Racemic and Optically Active Species

Hirofumi Nakamura
Abstract The complex [Co(H3L)](ClO4)3·H2O (1), where H3L {tris[2-(4-imidazoylmethylideneamino)ethyl]amine} is a tripodal ligand obtained by condensation of tris(2-aminoethyl)amine and 4-formylimidazole in a 1:3 molar ratio, was synthesized and optically resolved by fractional crystallization of the diastereomeric salt with [Sb2{(R,R)-tart}2]2, [(R,R)-tart = (2R,3R)-tartrate(4,) ion]. From the less soluble part, ,-[Co(H2L)][Sb2{(R,R)-tart}2]·4H2O (2) was isolated. Starting from 2, two optically active complexes, ,-[Co(H3L)](ClO4)3·1.5H2O (,- 1) and ,-[Co(L)] (,- 3), were obtained. The crystal structures of these complexes are compared with those of the racemic structures. ,- 1 shows an unusually strong circular dichroism (, = 488 nm, ,, = ,7.74 M,1,cm,1) in the first d,d absorption band region. The effects of deprotonation,reprotonation of the uncoordinated imidazole NH groups of ,-[Co(H3L)]3+ on the UV/Vis and CD spectra and on the cyclic voltammograms were studied in methanol. Although the deprotonation,reprotonation reactions are reversible, the redox couple for the completely deprotonated species [CoIII/II(L)]0/, is not observed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source]

Synthesis and Characterization of CuII Complexes with Amino Acid Substituted Di(2-pyridyl)amine Ligands

ko I. Kirin
Abstract The two-step syntheses of the substituted di(2-pyridyl)amine ligands (dpa), dpa-CH2CO2H (1) and dpa-PhCO2H (2), are described. Ligands 1 and 2 are successfully coupled to the amino acid phenylalanine, yielding the derivatives 4 and 6, respectively. Four CuII(dpa)2 complexes, [Cu(dpa-CH2CO2tBu)2(NO3)2] (3Cu), [Cu(dpa-CH2CO-PheOMe)2(H2O)2](NO3)2·2MeOH (4Cu), [Cu(dpa-PhCO2Me)2 (MeOH)2](ClO4)2 (5Cu) and [Cu(dpa-PhCO-PheOMe)2(ClO4)2] (6Cu) have been prepared and characterized, including their single crystal X-ray structures. Fluorescence emission at UV (for 3 and 4) or blue (for 5 and 6) wavelengths of the free ligands is preserved in the corresponding Cu complexes, although with lower intensity. X-band EPR spectra of 4Cu and 6Cu both revealed one axial CuII signal with hyperfine and superhyperfine splittings. Complexes 4Cu and 6Cu are chiral inorganic complexes with amino acid bioconjugates that may serve as nucleoside analogs in modified peptide nucleic acids (PNA). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

Tetranuclear Nickel Complexes Composed of Pairs of Dinuclear LNi2 Fragments Linked by 4,4,-Bipyrazolyl, 1,4-Bis(4,-pyrazolyl)benzene, and 4,4,-Bipyridazine: Synthesis, Structures, and Magnetic Properties

Vasile Lozan
Abstract The ability of the ligands 4,4,-bipyrazolyl (H2bpz), 1,4-bis(4,-pyrazolyl)benzene (H2bpzb), and 4,4,-bipyridazine (bpdz) to link two dioctahedral LNi2 units has been examined. Thefollowing complexes were prepared: [L1NiII2(Hbpz)][BPh4] (6[BPh4]), [L1NiII2(bpdz)][ClO4]2 (7[ClO4]2), [(L1NiII2)2(bpzb)][BPh4]2 (8[BPh4]2), and [(L2NiII2)2(bpz)][BPh4]2 (9[BPh4]2), where (L1)2, and (L2)2, represent macrocyclic hexaaza-dithiophenolate ligands. All complexes have been characterised by UV/Vis spectroscopy, IR spectroscopy, and X-ray crystallography. Whereas (Hbpz), and bpdz in 6[BPh4]2 and 7[ClO4]2 act as bidentate ligands coordinating to only one [LNi2]2+ unit, in 8[BPh4]2 and 9[BPh4]2 the (bpzb)2, and(bpz)2, units are tetradentate linkers. This is qualitatively explained in terms of the absence or presence of steric repulsions between the tBu groups of the supporting ligands and the length of the coligands. The structures of the tetranuclear complexes differ mainly in the distance between the center of the Ni···Ni axes of the isostructural [LNi2] units {14.040(1) Å in 8[BPh4]2, 9.184(1) Å in 9[BPh4]2}. The two Ni2pyrazolato planes in 9[BPh4]2 are coplanar. An analysis of the temperature-dependent magnetic susceptibility data for 9[BPh4]2 reveals the presence of weak ferromagnetic exchange interactions between the NiII ions in the binuclear [L2Ni2] subunits with values for the magnetic exchange constant J1 of 23.97 cm,1 (H = ,2JS1S2). The exchange coupling across the dipyrazolato bridge is less than 0.1 cm,1, suggesting that no significant interdimer exchange coupling occurs in 9[BPh4]2. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

Metal Ion Complementarity: Effect of Ring-Size Variation on the Conformation and Stability of Lead(II) and Cadmium(II) Complexes with Pendant-Armed Crowns

Martín Regueiro-Figueroa
Abstract The binding tendencies of the pendant-armed crown ethers L1,L3 [L1 = N,N, -bis(benzimidazol-2-ylmethyl)-1,7-diaza-12-crown-4, L2 = N,N, -bis(benzimidazol-2-ylmethyl)-1,10-diaza-15-crown-5) and L3 = N,N, -bis(benzimidazol-2-ylmethyl)-4,13-diaza-18-crown-6] towards PbII and CdII have been investigated. The X-ray crystal structure of [Cd(L3)](ClO4)2·EtOH shows that, in the solid state, the CdII ion is eight-coordinate and fits quite well into the crown hole, favouring an anti arrangement of the organic receptor. NMR measurements recorded in acetonitrile solution indicate that increasing the crown size induces a conformational change in the series of CdII complexes. The conformation goes from a syn arrangement for L1 to an anti arrangement for L3, passing through a syn [lrarr2] anti equilibrium in the complex derived from L2. On the contrary, no conformational change was observed for the corresponding PbII complexes, which have a syn conformation in all cases. These results have been confirmed by means of density functional theory (DFT) calculations performed by using the B3LYP model. The binding constants obtained from UV/Vis titration experiments in DMSO solution demonstrate that a decrease in the crown size provokes a 102 -fold enhancement of the stability for this series of CdII complexes, whereas for PbII a gradual decrease of the binding constants is observed. Receptor L1 shows a certain degree of selectivity for CdII over PbII, with a selectivity factor > 102. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

Synthesis, Crystal Structure, and Magnetic Properties of Two Manganese(II) Polymers Bearing Ferrocenecarboxylato Ligands

Zilu Chen
Abstract Reactions of Mn(ClO4)2·6H2O with FcCO2Na [Fc = (,5 -C5H4)Fe(,5 -C5H5)] in methanol solution gave [Mn3(FcCO2)6(CH3OH)4]n (1), and, in the presence of 4,4,-bipyridine (4,4,-bpy), [Mn3(FcCO2)6(H2O)2(4,4,-bpy)]n (2). Both complexes have the similar chains with a sequence of ,Mn,(,2 -COO)n,Mn,(,2 -COO),Mn,(,2 -COO),Mn,(,2 -COO)n,Mn, (n = 4 and 2 for complex 1 and 2, respectively), which are constructed alternatively from mononuclear [MnII] units and dinuclear [Mn2(FcCO2)4] units by ,2 -ferrocenecarboxylato- O,O, bridging. The two MnII ions in the dinuclear [Mn2(FcCO2)4] units of complex 1 are connected by four ferrocenecarboxylato ligands to form a swastika-like shaped skeleton, which is rare in metallocenecarboxylato complexes. However, the two MnII ions in the dinuclear [Mn2(FcCO2)4] units of complex 2 are bridged only by two carboxylato ligands, and the other two ferrocenecarboxylato ligands in this unit bind in a chelating mode. The chains in complex 2 are further interconnected by the coordinated 4,4,-bipyridine molecules to form two-dimensional coordination sheets. Magnetic susceptibility measurements revealed a weak antiferromagnetic coupling for both complexes. A model Heisenberg chain comprising classical spins coupled through alternating exchange interactions J1,J1,J2 (AF1,AF1,AF2) is proposed to describe the magnetic behavior. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

Receptor versus Counterion: Capability of N,N, -Bis(2-aminobenzyl)-diazacrowns for Giving Endo- and/or Exocyclic Coordination of ZnII

Lea Vaiana
Abstract The structure of ZnII complexes with receptors L1 and L2[L1 = N,N, -bis(2-aminobenzyl)-1,10-diaza-15-crown-5 and L2 = N,N, -bis(2-aminobenzyl)-4,13-diaza-18-crown-6] was studied both in the solid state and in acetonitrile solution. Both receptors form mononuclear ZnII complexes in this solvent, while no evidence for the formation of dinuclear complexes was obtained. This is in contrast with previous investigations that demonstrated the formation of dinuclear complexes of L2 with first-row transition metals such as NiII, CoII and CuII. Compounds of formula [Zn(L1)](ClO4)2 (1), [Zn(L1)](NO3)2·2CH3CN (2), [Zn(L2)](ClO4)2 (3) and [Zn(L2)(NO3)2] (4) were isolated and structurally characterised by X-ray diffraction analyses. L1 forms seven-coordinate ZnII complexes in the presence of both nitrate and perchlorate anions, as a consequence of the good fit between the macrocyclic cavity and the ionic radius of the metal ion. The ZnII ion is deeply buried into the receptor cavity and the anions are forced to remain out of the metal coordination sphere. The cation [Zn(L1)]2+ present in 1 and 2 is one of the very few examples of seven-coordinate Zn complexes. Receptor L2 provides a very rare example of a macrocyclic receptor allowing endocyclic and exocyclic coordination on the same guest cation, depending on the nature of the anion present. Thus, in 3 the ZnII ion is endocyclically coordinated, placed inside the crown hole coordinated to four donor atoms of the ligand in a distorted tetrahedral environment, whereas in 4, the presence of a strongly coordinating anion such as nitrate results in an exocyclic coordination of ZnII, which is directly bound only to the two primarily amine groups of L2 and two nitrate ligands. Spectrophotometric titrations of [Zn(L2)]2+ with tetrabutylammonium nitrate in acetonitrile solution demonstrate the stepwise formation of 1:1 and 1:2 adducts with this anion in acetonitrile solution. The [Zn(L1)]2+, [Zn(L2)]2+ and [Zn(L2)(NO3)2] systems were characterised by means of DFT calculations (B3LYP model). The calculated geometries show an excellent agreement with the experimental structures obtained from X-ray diffraction analyses. Calculated binding energies of the macrocyclic ligands to ZnII are also consistent with the experimental data.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

Transition Metal-Assisted Hydrolysis of Pyrazole-Appended Organooxotin Carboxylates Accompanied by Ligand Transfer

Vadapalli Chandrasekhar
Abstract The reaction of the potentially multi-site coordination ligands [{nBu2SnO2CL}2O]2 (1), [{nBu2SnO2CL,}2O]2 (2), [nBuSn(O)O2CL]6 (3), and [nBuSn(O)O2CL,]6 (4), (L = (Pz)2CH-); L, = (3,5-Me2Pz)2CH-; Pz = pyrazolyl) with hydrated metal salts leads to the hydrolysis of the organotin carboxylates accompanied by the formation of insoluble organotinoxide/hydroxides and metal complexes. The in situ generated LCOO and L,COO ligands bind to the metal ions. The complexes [Cu(LCOO)2(NO3)2(nBu2Sn((H2O)2)]n[Cu(LCOO)2] (5), [Mg(L,COO)2] (6), [Cu(LCOO)2] (7), and [{(Cu(L,COO)2(Cu(MeOH))3}{ClO4}2]n (8) were isolated and structurally characterized. The solid-state structure of 5 reveals that two discrete molecules are present in the same asymmetric unit; a heterobimetallic coordination polymer, [Cu(LCOO)2(NO3)2(nBu2Sn((H2O)2)]n and a discrete coordination complex, [Cu(LCOO)2]. The cationic portion of the heterobimetallic compound contains alternate six-coordinate SnIV and CuII centers bridged by the carboxylate oxygen atoms of the LCOO ligand.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

Anion-Dependent Structural Diversity in Silver(I) Complexes of 4-Amino-3,5-diisopropyl-1,2,4-triazole

Guang Yang
Abstract Reactions of silver salts with 4-amino-3,5-diisopropyl-1,2,4-triazole (L) afford dinuclear complex [Ag2L2(NO3)2(CH3CN)], triangular complex [Ag3L3](CF3SO3)3, and cyclic tetranuclear complexes [Ag4L6](BF4)4 and [Ag4L6](ClO4)4. On the basis of the X-ray analyses, anions are found to play an important role in determining the structures. Through coordination/noncoordination, anions can impart their influence on the coordination geometry of Ag atoms and the angles of N,Ag,N, which seems to be the main factor controlling the nuclearity of the reaction products in this system. 1H NMR and MS measurements suggest that these complexes probably retain their structural integrities in CH3CN solution. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

An Eight-Coordinate Mononuclear Double Helical Complex

Michael G. B. Drew
Abstract From the reaction of Cd(CH3COO)2·2H2O with the 1:2 condensate (L) of benzil dihydrazone and 2-acetylpyridine, [CdL(CH3COO)(H2O)]PF6·3H2O (1) is isolated by adding NH4PF6. L reacts with Cd(ClO4)2·xH2O to yield [CdL2](ClO4)2·0.5H2O (2). The yellowish complexes 1 and 2 are characterized by NMR and single-crystal X-ray diffraction. 1 is found to be a seven-coordinate single helical complex having a CdIIN4O3 core and homoleptic 2 an eight-coordinate double helical complex with a CdIIN8 core.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

Polymers or Supramolecules Generated From a New V-Shaped Bis-monodentate Ligand and the Effect of Steric Hindrance on Coordination Modes of the Ligand

Caihua Zhou
Abstract A new V-shaped bis-monodentate ligand L (L = 2,3,-dipyridylamine) (1) has been designed and synthesized by alkylation reaction of pyridylamine. An investigation of the charge distributions of the coordination atoms and single-point energy calculations of four conformers of ligand L based on the geometry of conformers optimized by the DFT (density functional theory) method was carried out. The results show that the four conformers of ligand L take on two stable and two less stable configurations. Theory forecasts that two relatively stable configurations present in complexes as probable coordination motifs of the ligand, and that steric hindrance of pyridine nitrogen atoms in isomers will affect its coordination ability together with the electronic factor. This forecast has been demonstrated by the coordination chemistry of ligand L, that is, configuration (a) and (b) of the ligand occur in the following reported complexes, which combines with AgI or CuII through two coordination modes (bidentate bridging or a monodentate mode) resulting in coordination polymers {[Ag (L)2]NO3}n (2), [Cu2(L)2(maa)4]n (maa = methacrylic acid) (3), and the mononuclear molecule [Cu(L)4](ClO4)2·2CH3CH2OH (4). The ligand assumes different coordination modes in the three complexes because of different levels of steric hindrance of the pyridine nitrogen atoms in the conformers. Interestingly, polymers 2 and 3 assume a 1D helical structure and a linear framework, respectively, and 4 has a 2D supramolecular architecture induced from hydrogen bond interactions. In addition, the magnetic properties of 3 have been explored, which shows a strong antiferromagnetic interaction.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

Synthesis, Characterization, and Properties of Some Copper(II) Complexes of 2-Pyridineformamide Thiosemicarbazone (HAm4DH)

María del Carmen Aguirre
Abstract Reactions between different copper(II) salts and 2-pyridineformamide thiosemicarbazone (HAm4DH) in neutral ethanolic media led to the formation of complexes with the formulae [Cu(HAm4DH)X2] (X = Cl or Br) (1, 2) and [Cu(HAm4DH)2]X2 (X = NO3 or ClO4) (3, 4). The same reactions carried out in the presence of triethylamine gave rise to new complexes with the general formulae [Cu(Am4DH)X] (X = Cl, Br, AcO, or NO3) (5,8), [Cu(H2O)(Am4DH)](ClO4) (9), and [Cu(Am4DH)2] (10), many of which were isolated with different molecules of crystallization and contain a deprotonated thiosemicarbazone (Am4DH). These complexes were characterized by elemental analysis, and different spectroscopic and magnetic techniques. The thermal and redox behavior of the complexes was also evaluated. Complexes 1, 2, 5, and 6 show better nuclease activity than [Cu(phen)2]2+. Inaddition, crystals were isolated in the cases of [Cu(HAm4DH)Cl2]2 (5a), 1,[Cu(Am4DH)Cl] (5b), 1,[Cu(Am4DH)Br] (6a), and [Cu(HAm4DH)(H2O)(ClO4)2]·MeOH·H2O (9a) and these structures were analyzed by X-ray diffraction. Compound 5a has a dimeric structure with chlorine bridges and shows weak antiferromagnetism (J = ,12.2 cm,1). Complexes 5b and 6a are one-dimensional polymers formed through halogen bridges and the deprotonated thiosemicarbazone in the thiolate form. In compound 9a the copper(II) is in a distorted octahedral environment with two ClO4 units coordinated to the metal center. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

Copper Complexes with (2,7-Di- tert -butylfluoren-9-ylidene)methanedithiolate: Oxidatively Promoted Dithioate Condensation,

José Vicente
Abstract The reaction of [Cu(NCMe)4]PF6 with piperidinium 2,7-di- tert -butyl-9H -fluorene-9-carbodithioate (pipH)[S2C(tBu-Hfy)] (1; tBu-Hfy = 2,7-di- tert -butylfluoren-9-yl), affords [Cun{S2C(tBu-Hfy)}n] (2), which reacts with various P ligands to give [Cu{S2C(tBu-Hfy)}L2] [L = PPh3 (3a), PCy3 (3b), PiPr3 (3d); L2 = 1,1,-bis(diphenylphosphanyl)ferrocene (dppf, 3c), bis(diphenylphosphanyl)methane (dppm, 3e)]. Compounds 3a,c react with atmospheric oxygen and moisture in the presence of NEt3 to give the dinuclear complexes [Cu2{[SC=(tBu-fy)]2S}L2] [tBu-fy = 2,7-di- tert -butylfluoren-9-ylidene; L = PPh3 (4a), PCy3 (4b); L2 = dppf (4c)], which contain a new dithiolato ligand formally resulting from the condensation of two dithioato ligands with loss of a sulfide ion and two protons. Neutral CuI dithiolate complexes of the type [Cu4{S2C=(tBu-fy)}2L4] [S2C=(tBu-fy) = [2,7-di- tert -butylfluoren-9-ylidene)methanedithiolate; L = PPh3 (5a), P(C6H4OMe- p)3 (5b), PiPr3 (5d) or L2 = dppf (5c)] were obtained by treating 1 with [Cu(NCMe)4]PF6, the corresponding phosphane, and piperidine in a 1:2:2:1 molar ratio. The reaction of 1 with Cu(ClO4)2·6H2O and (Pr4N)OH in a 2:1:2 molar ratio gives the CuII complex (Pr4N)2[Cu{S2C=(tBu-fy)}2] [(Pr4N)26], which readily oxidizes to the CuIII complex Pr4N[Cu{S2C=(tBu-fy)}2] (Pr4N7) in the presence of atmospheric oxygen and moisture. The salt PPN7 [PPN+ =(Ph3P)2N+] was obtained from 1, CuCl2·2H2O, PPNCl, and piperidine in a 2:1:1:2 molar ratio under aerobic conditions. The crystal structures of 3a, 3c·CH2Cl2, 4a·4Me2CO, and 4c·CH2Cl2 have been determined by X-ray diffraction studies. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

Synthesis, Structure and Spectroscopic Properties of Novel9,10-Bis{[6-(diphenylphosphanyl)-2-pyridylmethyl]propylaminomethyl}anthracene-Bridged Group 11 Metal (M = CuI and AgI) Dinuclear Complexes

Hu Xu
Abstract Dinuclear complexes [M2(,-BPNNAn)]X2 (M = CuI, X = ClO4,1, X = BF4,2; M = AgI, X = BF4,3, X = ClO4,4) have been prepared by treating 9,10-bis{[6-(diphenylphosphanyl)-2-pyridylmethyl]propylaminomethyl}anthracene (BPNNAn) with M(CH3CN)4X in CH2Cl2. The structures of complexes 1, 2 and 3 have been determined by single-crystal X-ray diffraction studies. In the complexes, BPNNAn acts as a chelating ligand and two metal ions riding on two bridgehead carbon atoms in the anthracene group leads to the deformation of the anthracenyl ring. The Cu,Arene charge transfer interaction is observed from the nonfluorescent emission of Cu complex 1, while the Ag complex 3 exhibits dual emission at high concentrations in a CH2Cl2 solution. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]

A New Spherical Metallacryptate Compound [Na{Cu6(Thr)8(H2O)2(ClO4)4}]·ClO4·5,H2O: Magnetic Properties and DFT Calculations

Sheng-Chang Xiang
Abstract The hexanuclear copper(II) complex with threoninato acid has been synthesized. Its structure can be described as an octahedron cage with D2h symmetry in which six copper ions are bound by eight threoninato acids with a [3.11223130] coordination mode and one Na+ cation being captured within the center of the cage. In contrast with other hexanuclear copper compounds containing amino acids, the title compound has a prolate Cu6 octahedron with the longest axial distance and a rectangle equatorial plane, as well as special coordinated perchlorate ions. Compared with classic cryptate, hexanuclear copper(II) compounds with amino acids can be regarded as a new topologic type of spherical macrotricyclic metallacryptates [2,2,2,2] whose cages have a high selectivity for sodium ions. The analysis of magnetic susceptibility data shows that the threoninato compound has a ground state with spin S = 3. The computing coupling constant between the equatorial Cu centers and the axial ones is 4.4 cm,1,calculated by using DFT methods for a model compound. This is close to three known experimental values of 1.39, 0.56 or 0.43 cm,1 for complexes with 4-hydroxy- L -prolinato, L -prolinato or L -threoninato acid as ligands, respectively. The dominant ferromagnetic interactions for these complexes can be essentially attributed to the orthogonality between the magnetic orbitals, dxz or dyz orbitals for the equatorial CuII centers and d orbitals for the axial ones. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]

Mono- and Dinuclear CuII and ZnII Complexes of Cyclen-Based Bis(macrocycles) Containing Two Aminoalkyl Pendant Arms of Different Lengths

Carmen Anda
Abstract The basicity and coordination properties towards CuII and ZnII of the bis(macrocycles) L1, L2 and L3 have been investigated by means of potentiometric, 1H NMR and UV/Vis spectroscopic titrations in aqueous solutions. The synthesis of L1 and L3 is also described. The three ligands are composed of two [12]aneN4 units separated by a p- phenylene spacer and differ in the length of the aminoalkyl pendant arms linked to each macrocyclic unit. L1,L3 form mono- and dinuclear complexes in aqueous solutions; in the dinuclear species each metal ion is coordinated by one of the two identical [12]aneN4 ligand moieties, as shown by the crystal structures of the complexes [Cu2L1]Cl4·8H2O, [Zn2L2](ClO4)4 and [Zn2L3](ClO4)4·H2O. In all structures the metal ion is pentacoordinate, and is bound to the four nitrogen donors of the cyclic unit and to the amine group of the side arm. The stability of both the [ML]2+ and [M2L]4+ complexes in aqueous solution decreases in the order L1 > L2 > L3. At the same time, both the [Cu2L]4+ and [Zn2L]4+ complexes show a different ability in proton binding among the three ligands, with the [M2L1]4+ complexes displaying the highest basicity. These results are explained in terms of the decreasing number of nitrogen donors involved in CuII or ZnII binding on passing from L1 to L3; in other words, while in the L1 dinuclear complexes each metal ion is coordinated to the four amine groups of a [12]aneN4 moiety and to the amine group of the side arm, in the L3 ones the metal cations are bound only to the four donor atoms of a cyclic moiety, the aminobutyl group not being coordinated. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]