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PubMed2001

4-Cyanopyridine and amide-N and amide-O linkage isomers of 4-pyridinecarboxamide on trans-chloro(1,4,8,11-tetraazacyclotetradecane)ruthenium(II/III).

The synthesis, UV-vis spectra, and electrochemical behavior of the nitrile-bonded trans-[Ru(II)Cl(cyclam)(4-NCpyH(+))](BF(4))(2) (4-Ncpy = 4-cyanopyridine; cyclam = 1,4,8,11-tetraazacyclotetradecane) and of trans-[Ru(III)Cl(cyclam)(NHC(O)-4-pyH(+))](2+) are described. The UV-vis spectrum of the Ru(II) nitrile complex shows a MLCT band at 548 nm at pH 1, which is shifted to 440 nm at pH approximately 6, for the unprotonated species. trans-[Ru(II)Cl(cyclam)(4-NCpyH(+))](2+) was electrolytically oxidized (+600 mV vs Ag/AgCl) at pH 1 to Ru(III), followed by hydrolysis (k = 0.25 s(-1)) of the coordinated nitrile to give trans-[Ru(III)Cl(cyclam)(NHC(O)-4-pyH(+))](2+), in which the amide is deprotonated and coordinated through nitrogen. The identity of the species is pH dependent, the nitrogen-bonded amide prevailing at low pH (< 7), but the oxygen-bonded amide is formed through linkage isomerization at higher pH (>8). Reduction of trans-[Ru(III)Cl(cyclam)(NHC(O)-4-pyH)](2+) in acidic media does not result in fast aquation (k = approximately 2.4 x 10(-5) s(-1)) as for other amides on ruthenium(II) pentaammine, but instead linkage isomerization occurs, resulting in the oxygen-bonded species, with an estimated rate constant of approximately 2 x 10(-2) s(-1), smaller than in the pentaammine analogues.

Journal Article↗
PubMed2003

Metal ion enhanced binding of AMD3100 to Asp262 in the CXCR4 receptor.

The affinity of AMD3100, a symmetrical nonpeptide antagonist composed of two 1,4,8,11-tetraazacyclotetradecane (cyclam) rings connected through a 1,4-dimethylene(phenylene) linker to the CXCR4 chemokine receptor was increased 7, 36, and 50-fold, respectively, by incorporation of the following: Cu(2+), Zn(2+), or Ni(2+) into the cyclam rings of the compound. The rank order of the transition metal ions correlated with the calculated binding energy between free acetate and the metal ions coordinated in a cyclam ring. Construction of AMD3100 substituted with only a single Cu(2+) or Ni(2+) ion demonstrated that the increase in binding affinity of the metal ion substituted bicyclam is achieved through an enhanced interaction of just one of the ring systems. Mutational analysis of potential metal ion binding residues in the main ligand binding crevice of the CXCR4 receptor showed that although binding of the bicyclam is dependent on both Asp(171) and Asp(262), the enhancing effect of the metal ion was selectively eliminated by substitution of Asp(262) located at the extracellular end of TM-VI. It is concluded that the increased binding affinity of the metal ion substituted AMD3100 is obtained through enhanced interaction of one of the cyclam ring systems with the carboxylate group of Asp(262). It is suggested that this occurs through a strong concomitant interaction of one of the oxygen's directly with the metal ion and the other oxygen to one of the nitrogens of the cyclam ring through a hydrogen bond.

Amino Acid Sequence↗
PubMed2002

Structure and dynamics of metallomacrocycles: recognition of zinc xylyl-bicyclam by an HIV coreceptor.

As platforms for the design of metal-based therapeutic and diagnostic agents, macrocycles are rigid enough to provide strong metal binding sites and orient functional groups stereoselectively, yet flexible enough to accommodate structural changes required for induced-fit recognition of biological targets. We consider the recognition of the Zn(II) complex of the bis-tetraazamacrocycle xylyl-bicyclam, a potent anti-HIV agent, by the coreceptor CXCR4, a G-protein-coupled receptor used by HIV for membrane fusion and cell entry. NMR studies show that the macrocycles of Zn(II)(2)-xylyl-bicyclam perchlorate exist in aqueous solution as two major configurations, trans-I (nitrogen chirality R,S,R,S), and trans-III (S,S,R,R). Acetate addition induced a major structural change. X-ray crystallography shows that the acetate complex contains the unusual cis-V cyclam configuration (R,R,R,R and folded) with bidentate coordination of acetate to Zn(II) plus second-coordination-sphere double H-bond formation between diagonal NH protons on the opposite cyclam face and acetate carboxylate oxygens. Detailed 1D and 2D NMR studies show that the major configuration of Zn(II)(2)-xylyl-bicyclam acetate in aqueous solution is cis-V/trans-I. Molecular modeling shows that an analogous cis-V site can be formed when Zn(II)(2)-xylyl-bicyclam binds to CXCR4, involving the carboxylate groups of Asp262 (Zn(II) coordination) and Glu288 (double H-bonding). The second cyclam can adopt the trans-I (or trans-III) configuration with Zn(II) binding to Asp171. These interactions are consistent with the known structure-activity relationships for bicyclam anti-HIV activity and receptor mutation. Consideration of the anti-HIV activity of xylyl-bicyclam complexes of other metal ions suggests that affinity for carboxylates, configurational flexibility, and kinetic factors may all play roles in receptor recognition. For example, Pd(II) cyclam complexes interact only weakly with axial ligands and are inflexible and inactive, whereas Co(III) cyclams bind carboxylates strongly, are configurationally flexible, and yet have low activity. Our findings should aid the design of new generations of active macrocycles including highly specific chemokine receptor antagonists.

Benzylamines↗
PubMed1987

Effects of treatment with N-methyl-N-nitrosourea, artificial sweeteners, and cyclophosphamide on adult rat urinary bladder in vitro.

The effect of N-methyl-N-nitrosourea (MNU), sodium saccharin, sodium cyclamate and cyclophosphamide on rat bladder explants in vitro was studied. MNU administered as a single dose or in multiple treatments induced concentration-dependent changes in urothelial ultrastructure and cell surface topography. In a single treatment protocol, extensive cytotoxicity was observed in both the urothelium and stroma at concentrations of 500 to 1000 micrograms/ml, establishing a toxic threshold within this range. In a multiple treatment protocol, repeated doses of low concentrations of carcinogen (7 or 8 x 50 micrograms/ml, 6 x 100 micrograms/ml) induced hyperplastic and dysplastic changes in the urothelium with no cytotoxicity, but cytotoxic effects were observed following treatments of 4 x 200 micrograms/ml or 2 x 400 micrograms/ml. Sodium saccharin, sodium cyclamate, and cyclophosphamide induced changes in urothelial cell surface topography consistent with hyperplasia and preneoplasia. Prolonged exposure to saccharin or cyclamate followed by a single dose of MNU elicited more extensive abnormalities in the urothelium than either saccharin or cyclamate alone, suggesting that these artificial sweeteners have initiating activity in a multistage process. The ultrastructural changes induced by in vitro treatment showed a good correlation with the pathological changes observed in vivo in rats treated with MNU or fed either with saccharin or cyclamate.

Animals↗
PubMed1996

Study of the Reactions of Platinum Macrocyclic Complex Ions with Free Radicals Formed by Pulse Radiolysis of Aqueous Media.

The near-diffusion-controlled reactions of hydroxyl radical, hydrated electron, and hydrogen atom with platinum macrocyclic complex ions in aqueous media have been studied using pulse radiolysis in conjunction with UV-visible absorption and conductivity detection. The hydrated electron and hydrogen atom react with trans-[Pt(cyclam)(Cl)(2)](2+) where cyclam is 1,4,8,11-tetraazacyclotetradecane to yield platinum(III) transients that exhibit intense absorption peaks in the 280-300 nm region; however in the case of the H-atom, the reaction involves a competition between chloride abstraction and a minor process, suggested to be attack on the organic ligand. The platinum(III) products are kinetically labile toward loss of chloro ligands, but these reactions are reversible in the presence of added KCl. The reactions of hydroxyl radical with [Pt(cyclam)](2+) and with [Pt(tmc)](2+), where tmc is 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, lead to platinum(III) intermediates absorbing in the 250-300 nm region. Depending on the presence or absence of added KCl and on the pH, the platinum(III) cyclam systems can react to form a product(s) exhibiting absorption peaks near 330 and 455 nm, and this species is proposed to be a long-lived amidoplatinum(III) complex. In support of this proposal is the observation that the tmc system does not give rise to a similar visible-absorbing product. The interrelations of the cyclam-based transients through acid-base, chloro-substitution and water-elimination processes are discussed.

Journal Article↗
PubMed2005

Probing shapes of bichromophoric metal-organic complexes using ion mobility mass spectrometry.

Ion mobility mass spectrometry (IM-MS) was used to probe the structures of several metal complexes carrying pendant chromophores. The three complexes investigated were the copper(II) complex Cu(DAC)2+ (DAC = 1,8-bis(9-methylanthracyl)cyclam, cyclam = 1,4,8,11-tetraazacyclotetradecane), the N-nitrosylated ligand DAC-NO, and the Roussin's red salt ester (mu-S,mu-S')-protoporphyrin-IX-bis(2-thioethyl ester)tetranitrosyldiiron (PPIX-RSE). From the IM-MS data coupled with theoretical calculations, it was found that [Cu(II)(DAC - H)]+ exists as a single conformer, with one anthracenyl group above the cyclam and the other below, similar to the crystal structure of Cu(II)(DAC)2+. The metal-free N-nitrosylated ligand (DAC-NO + H)+ has two conformations: one family of structures has one anthracenyl group above the cyclam and one below, while the other has both anthracenyl groups on the same side of the cyclam. These observations are consistent with 1H NMR data for the neutral DAC-NO complex that indicate the presence of two geometric isomers in solution. The third species, PPIX-RSE, has a porphyrin chromophore covalently linked to an Fe2S2(NO)4 cluster for use as a precursor for the photochemical delivery of nitric oxide in single- and two-photon excitation processes. Ion mobility indicates the presence of two (PPIX-RSE + H)+ conformations, consistent with the previous interpretation of the bimodal fluorescence lifetime decay seen for PPIX-RSE. DFT structures, in good agreement with the IM-MS cross sections, indicate two "bent" conformations with the planes of the porphyrin and Fe2S2 rings at different angles with respect to each other.

Journal Article↗
PubMed2005

Exchange coupling across the cyanide bridge: structural and DFT interpretation of the magnetic properties of a binuclear chromium(III) complex.

The reaction of [Cr(CN)6]3- with a mixture of trans-[Cr(cyclam)(OH)2]Cl, [Cr(cyclam)(OH)Cl]Cl and [Cr(cyclam)Cl2]Cl affords the cyanide bridged dimer, trans-[HO-Cr(cyclam)-NC-Cr(CN)5]-. The tetraphenylphosphonium salt of the anion crystallizes in space group P2(1)/n and shows a bent arrangement of the Cr1-CN-Cr2 unit with the Cr1-CN bond angle at 166.9 degrees and CN-Cr2 at 160.32 degrees . The Cr2-O bond, trans to the hexacyanide fragment, is very short at 1.902 A. Two dimers are held together by two hydrogen bonds connecting the Cr2-OH group of each dimer with one of the NH groups of the cyclam ligand of an adjacent molecule, leading to an almost linear configuration. These dimers of dimers get packed parallel to each other, generating layers separated by the tetraphenylphosphonium cations. Four of the cyanide groups of the anion are engaged in H-bonds with the four water molecules present in the structure or with a NH group of the macrocycle of an adjacent molecule. From magnetic susceptibility measurements, the dimer was found to exhibit antiferromagnetic interaction between the Cr(III) centers with J=-16 cm(-1)(H=-2JS(A)S(B)). Structural and magnetic parameters have been calculated by density functional theoretical methods at the B3LYP level. The exchange coupling constant, J, calculated for the dimer at the X-ray geometry is -23.2 cm(-1) which is in excellent agreement with the experimental value.

Chromium↗
PubMed2006

Magnetic anisotropy of two trinuclear and tetranuclear Cr(III)Ni(II) cyanide-bridged complexes with spin ground states S = 4 and 5.

The trinuclear and the tetranuclear complexes [[iPrtacnCr(CN)3]2[Ni(cyclam)]](NO3)2.5H2O 1 (cyclam = 1,4,8,11-tetraazacyclotetradecane, iPrtacn = 1,4,7-tris-isopropyl-1,4,7-triazacyclononane) and [[iPrtacnCr(CN)3Ni(Me2bpy)2]2](ClO4)4.2CH3CN 2 (Me2bpy = 4,4-dimethyl-2,2-bipyridine) were synthesized by reacting (iPrtacn)Cr(CN)3 with [Ni(cyclam)](NO3)2 and [Ni(Me2bpy)2(H2O)2](ClO4)2, respectively. The crystallographic structure of the two compounds was solved. The molecular structure of complex 1 consists of a linear Cr-Ni-Cr arrangement with a central Ni(cyclam) unit surrounded by two Cr(iPrtacn)(CN)3 molecules through bridging cyanides. Each peripheral chromium complex has two pending CN ligands. Complex 2 has a square planar arrangement with the metal ions occupying the vertices of the square. Each Cr(iPrtacn)(CN)3 molecule has two bridging and one non-bridging cyanide ligands. The magnetic properties of the two complexes were investigated by susceptibility vs. temperature and magnetization vs. field studies. As expected from the orthogonality of the magnetic orbitals between Cr(III) (t2g3) and Ni(II) (e(g)2) metal ions, a ferromagnetic exchange interaction occurs leading to a spin ground states S = 4 and 5 for 1 and 2, respectively. The magnetization vs. field studies at T = 2, 3 and 4 K showed the presence of a magnetic anisotropy within the ground spin states leading to zero-field splitting parameters obtained by fitting the data D4 = 0.36 cm(-1) and D5 = 0.19 cm(-1) (the indices 4 and 5 refer to the ground states of complexes 1 and 2, respectively). In order to quantify precisely the magnitude of the axial (D) and the rhombic (E) anisotropy parameters, High-field high frequency electron paramagnetic resonance (HF-HFEPR) experiments were carried out. The best simulation of the experimental spectra (at 190 and 285 GHz) gave the following parameters for 1: D4 = 0.312 cm(-1), E4/D4 = 0.01, g4x = 2.003, g4y = 2.017 and g4z = 2.015. For complex 2 two sets of parameters could be extracted from the EPR spectra because a doubling of the resonances were observed and assigned to the presence of complexes with slightly different structures at low temperature: D5 = 0.154 (0.13) cm(-1), E5/D5 = 0.31 (0.31) cm(-1), g4x = 2.04 (2.05), g4y = 2.05 (2.05) and g4z = 2.03 (2.02). The knowledge of the magnetic anisotropy parameters of the mononuclear Cr(iPrtacn)(CN)3, Ni(cyclam)(NCS)2 and Ni(bpy)2(NCS)2 complexes by combining HF-HFEPR studies and calculation using a software based on the angular overlap model (AOM) allowed to determine the orientation of the local D tensors of the metal ions forming the polynuclear complexes. We, subsequently, show that the anisotropy parameters of the polynuclear complexes computed from the projection of the local tensors are in excellent agreement with the experimental ones extracted from the EPR experiments.

Journal Article↗
PubMed2006

Mechanism of iodide transport in the rabbit cortical collecting duct.

BACKGROUND: Pendrin, an anion exchanger known to participate in iodide transport in the apical membrane of follicular cells of the thyroid gland, has recently been shown to exist in the apical membrane of the beta- and gamma-intercalated (beta/gamma-IC) cells of the cortical collecting duct (CCD). We examined mechanisms of iodide transport in the CCD. METHODS: Rabbit CCD was perfused in vitro, and lumen-to-bath flux coefficients for both (125)I(-) (K(I (lb))) and (36)Cl(-) (K(Cl (lb))) were measured simultaneously. The intracellular pH (pHi) of beta/gamma-IC cells in the perfused CCD was measured by microscopic fluorometory, by loading 2',7'-bis-(2-carboxyethyl)-5(6)-carboxyfluorescein tetraacetoxy methylester (BCECF-AM), a fluorescent marker for pHi. The effects on pHi of the replacement of NaCl with Na cyclamate, NaI, or NaBr in the lumen or bath were observed. RESULTS: K(I (lb)) was comparable to or slightly higher than K(Cl (lb)). Both iodide and chloride in the lumen caused self- and cross-inhibitions to both fluxes. The addition of 5-nitro-2-(-3-phenylpropylamino)-benzoate (NPPB), a Cl(-) channel inhibitor, to the bath significantly reduced K(Cl (lb)), but not K(I (lb)). Replacement of luminal fluid NaCl with Na cyclamate, NaI, or NaBr caused alkalization of pHi, no change in pHi, and slight acidification of pHi, respectively. Replacement of bath NaCl with Na cyclamate, NaI, or NaBr caused alkalization, alkalization, and acidification of pHi, respectively. Luminal NaI prevented the acidification of pHi caused by bath Na cyclamate. CONCLUSIONS: The data are consistent with the model that iodide is transported via the Cl(-)/HCO(3) (-) exchanger in the apical membrane of beta/gamma-IC cells and exits the basolateral membrane via an electroneutral transporter that is distinct from the Cl(-) channel. We could not, however, identify which type of beta/gamma-IC cell was mainly responsible.

Animals↗
PubMed1973

Carcinogen-induced chromosomal breakage decreased by antioxidants.

Blood leukocyte cultures were incubated with antioxidants and the carcinogens sodium cyclamate and 7,12-dimethylbenz(alpha)anthracene in different combinations. There were 17.4% more chromosomal breaks in the group of cells treated with dimethylbenzanthracene only than in the untreated controls. The reductions in chromosomal breaks by the antioxidants were as follows: ascorbic acid, 31.7%; butylated hydroxytoluene, 63.8%; Na(2)SeO(3), 42.0%; and dl-alpha-tocopherol, 63.2%. Multiple chromosomal breaks were distributed equally throughout the experimental groups. Sodium cyclamate had only slightly more chromosomal breaks than the controls (11.6 compared to 10.9%). In the cyclamate groups treated with Na(2)SeO(3), 11.2% of chromosomes were broken. More acrocentric-type chromosomal breaks (21.7%) were seen in the untreated cells than the cells treated with cyclamate (3.4%) or dimethylbenzanthracene alone (4.8%). The carcinogen-treated groups had a higher percentage of meta breaks than the untreated controls.

Adult↗
PubMed2005

Potential clinical applications of the CXCR4 antagonist bicyclam AMD3100.

The bicyclam AMD3100 (originally called JM3100), in which the two cyclam rings are tethered by an aromatic bridge, emanated from JM2763, where the two cyclam moieties are tethered by an aliphatic linker - JM2763 in turn originated from JM1657, where the cyclam rings are directly linked to one another via a C-C bridge, and which was identified as an impurity, showing anti-HIV activity, in a commercial cyclam preparation. AMD3100 proved very effective against HIV-1 and HIV-2, inhibiting virus replication within the nM range, without toxicity for the host cells at concentrations that were > 100,000-fold higher than those required to inhibit HIV replication. The anti-HIV activity of AMD3100 appeared to be confined to the T-lymphotropic (X4) HIV strains, i.e. those strains that use the CXCR4 receptor to enter their target cells, and AMD3100 as of today still stands as one of the most potent and selective CXCR4 antagonists ever discovered. Hence, AMD3100 was found to interfere with a number of (patho)physiological processes which depend on the interaction of CXCR4 with its natural ligand, stromal derived factor (SDF-1) and which play an important role in rheumatoid, allergic and malignant diseases. AMD3100 has been shown to mobilize CD34+ stem cells from the bone marrow into the bloodstream and has also been shown to augment migration of bone marrow-derived endothelial progenitor cells into sites of neovascularization after myocardial infarction. Currently, AMD3100 is actively pursued as a stem cell mobilizer for transplantation in patients with multiple myeloma and non-Hodgkin's lymphoma.

Animals↗
PubMed1987

Evaluation of chelating drugs on the toxicity, excretion, and distribution of nickel in poisoned rats.

The effects of various doses of two macrocyclic drugs, namely, 1,4,8,11-tetraazacyclotetradecane (Cyclam) and 5,7,7',12,14,14'-hexamethyl-1,4,8,11-tetraazacyclotetradecane++ + (Cyclam s), on the toxicity, distribution, and excretion of nickel were evaluated in nickel-poisoned rats and compared with the linear counterpart triethylenetetraamine (TETA) and a tripeptide, glutathione (GSH). Cyclam and Cyclam s revealed a higher order of efficacy against the lethal response of nickel even at a lower dose. These drugs significantly enhanced the urinary and biliary excretion of nickel and restored the altered levels of trace metals (viz., Cu, Zn, Fe, Mn) compared to TETA and GSH. The efficacy of these drugs in vivo may be related to their ability to transport nickel across an artificial lipid membrane, a phenomenon was not exhibited by TETA or GSH.

Animals↗
PubMed2006

The macrocyclic effect and vasodilation response based on the photoinduced nitric oxide release from trans-[RuCl(tetraazamacrocycle)NO](2+).

Irradiation of trans-[RuCl(cyclam)(NO)](2+), cyclam is 1,4,8,11-tetraazacyclotetradecane, at pHs 1-7.4, with near UV light results in the release of NO and formation of trans-[Ru(III)Cl(OH)(cyclam)](+) with pH dependent quantum yields (from approximately 0.01 to 0.16 mol Einstein(-1)) lower than that for trans-[RuCl([15]aneN(4))(NO)](2+), [15]aneN(4) is 1,4,8,12-tetaazacyclopentadecane, (0.61 mol Einstein(-1)). After irradiation with 355 nm light, the trans-[RuCl([15]aneN(4))(NO)](2+) induces relaxation of the aortic ring, whereas the trans-[RuCl(cyclam)(NO)](2+) complex does not. The relaxation observed with trans-[RuCl([15]aneN(4))(NO)](2+) is consistent with a larger quantum yield of release of NO from this complex.

Animals↗
PubMed2002

Antiferromagnetic coupling in a six-coordinate high spin cobalt(II)-semiquinonato complex.

The 3,5-di-tert-butyl-catecholato and 9,10-phenanthrenecatecholato adducts of the cobalt-tetraazamacrocycle complex Co(Me(4)cyclam)(2+) (Me(4)cyclam = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) were synthesized and oxidized. The oxidation reaction products were isolated in the solid state as hexafluorophosphate derivatives. Both these complexes can be formulated as 1:1 cobalt(II)-semiquinonato complexes, that is, Co(Me(4)cyclam)(DBSQ)PF(6) (1) and Co(Me(4)cyclam)(PhSQ)PF(6) (2), in the temperature range 4-300 K, in striking contrast with the charge distribution found in similar adducts formed by related tetraazamacrocycles. The synthesis strategy and the structural, spectroscopic, and magnetic properties are reported and discussed. The crystallographic data for 2 are as follows: monoclinic, space group P2(1)/a, nomicron. 14, a = 14.087(4) A, b = 15.873(4) A, c = 14.263 (7) A, alpha = 89.91(3) degrees, beta = 107.34(2) degrees, gamma = 90.08(2) degrees, Z = 4. Both these complexes are characterized by triplet electronic ground states arising from the antiferromagnetic coupling between the high-spin d(7) metal ion and the radical ligand.

Journal Article↗
PubMed2005

Novel examples of high-dimensional mixed-valence copper cyanide complexes.

The first examples of high-dimensional mixed-valence homometallic cyano-bridged copper complexes were synthesized and characterized: net-structured [Cu(CN)(4){Cu(cyclam)}(1.5)](2)(n)()(H(2)O)(5)(n) (1), ladder-type double-chain-structured [Cu(CN)(2){Cu(CN)(2)Cu(cyclam)}](n)()(H(2)O)(n) (2), layer-structured [{Cu(CN)(2)}(2)Cu(cycalm)](n) (3), and hydrogen-bond-based 2-D [Cu(CN)(3)Cu(cyclam)](n)()(CH(3)OH)(n) (4) (cyclam = 1,4,8,11-tetraazacyclotetradecane). (1) Crystallizes in triclinic space group P with a = 8.3589(11) A, b = 13.478(2) A, c = 14.828(2) A, alpha = 66.895(2) degrees , beta = 77.916(3) degrees , gamma = 85.939(3) degrees , and Z = 1; (2) crystallizes in triclinic space group P with a = 8.2305(12) A, b = 9.8861(15) A, c = 13.219(2) A, alpha = 84.863(3) degrees , beta = 75.744(3) degrees , gamma = 89.818(3) degrees , and Z = 2; 3 crystallizes in monoclinic space group P2(1)/c with a = 6.830(2) A, b = 8.482(2) A, c = 17.306(4) A, beta = 98.144(4) degrees , and Z = 2; 4 crystallizes in triclinic space group P with a = 9.470(1) A, b = 10.034(1) A, c = 12.064(1) A, alpha = 67.325(2), beta = 75.593(2), gamma = 70.672(2), and Z = 2. The coordination sphere of Cu(I) sites in the complexes shows diverse structures: tetrahedral [CuC(4)] for (1), tetrahedral [CuC(3)N] and triangular [CuC(2)N] for (2), triangular [CuC(2)N] for (3), and triangular [CuC(3)] for 4. In particular, (1) constitutes the first example of a structurally characterized system containing a bridging tetrahedral [Cu(CN)(4)](3)(-) unit. The diverse structural nature of these complexes is governed by the capping amines and the content of water in the reaction media. The magnetic interactions are negligible in these mixed-valence complexes.

Journal Article↗
PubMed1996

Syntheses and Crystal Structures of Ruthenium Complexes of 1,4,8,11-Tetraazacyclotetradecane, Tris(2-aminoethyl)amine (tren), and Bis(2-aminoethyl)(iminomethyl)amine. A Microporous Layered Structure Consisting of {[K(tren)](2)[RuCl(6)]}(n)()(n)()(-) and {(H(5)O(2))(4)[RuCl(6)]}(n)()(n)()(+).

The second method for the synthesis of cis-[Ru(III)Cl(2)(cyclam)]Cl (1) (cyclam = 1,4,8,11-tetraazacyclotetradecane), with use of cis-Ru(II)Cl(2)(DMSO)(4) (DMSO = dimethyl sulfoxide) as a starting complex, is reported together with the synthesis of [Ru(II)(cyclam)(bpy)](BF(4))(2).H(2)O (2) (bpy = 2,2'-bipyridine) from 1. The syntheses of Ru complexes of tris(2-aminoethyl)amine (tren) are also reported. A reaction between K(3)[Ru(III)(ox)(3)] (ox = oxalate) and tren affords fac-[Ru(III)Cl(3)(trenH)]Cl.(1)/(2)H(2)O (3) (trenH = bis(2-aminoethyl)(2-ammonioethyl)amine = monoprotonated tren) and (H(5)O(2))(2)[K(tren)][Ru(III)Cl(6)] (4) as major products and gives fac-[Ru(III)Cl(ox)(trenH)]Cl.(3)/(2)H(2)O (5) in very low reproducibility. A reaction between 3 and bpy affords [Ru(II)(baia)(bpy)](BF(4))(2) (6) (baia = bis(2-aminoethyl)(iminomethyl)amine), in which tren undergoes a selective dehydrogenation into baia. The crystal structures of 2-6 have been determined by X-ray diffraction, and their structural features are discussed in detail. Crystallographic data are as follows: 2, RuF(8)ON(6)C(20)B(2)H(34), monoclinic, space group P2(1)/c with a = 12.448(3) Å, b = 13.200(7) Å, c = 17.973(4) Å, beta = 104.28(2) degrees, V = 2862(2) Å(3), and Z = 4; 3, RuCl(4)O(0.5)N(4)C(6)H(20), monoclinic, space group P2(1)/a with a = 13.731(2) Å, b = 14.319(4) Å, c = 13.949(2) Å, beta = 90.77(1) degrees, V = 2742(1) Å(3), and Z = 8; 4, RuKCl(6)O(4)N(4)C(6)H(28), trigonal, space group R&thremacr; with a = 10.254(4), c = 35.03(1) Å, V = 3190(2) Å(3), and Z = 6; 5, RuCl(2)O(5.5)N(4)C(8)H(22), triclinic, space group P&onemacr; with a = 10.336(2) Å, b = 14.835(2) Å, c = 10.234(1) Å, alpha = 90.28(1) degrees, beta = 90.99(1) degrees, gamma = 92.07(1) degrees, V = 1567.9(4) Å(3), and Z = 4; 6, RuF(8)N(6)C(16)B(2)H(24), monoclinic, space group P2(1)/c, a = 10.779(2) Å, b = 14.416(3) Å, c = 14.190(2) Å, beta = 93.75(2) degrees, V = 2200.3(7) Å(3), and Z = 4. Compound 4 possesses a very unique layered structure made up of both anionic and cationic slabs, {[K(tren)](2)[Ru(III)Cl(6)]}(n)()(n)()(-) and {(H(5)O(2))(4)[Ru(III)Cl(6)]}(n)()(n)()(+) (n = infinity), in which both sheets {[K(tren)](2)}(n)()(2)(n)()(+) and {(H(5)O(2))(4)}(n)()(4)(n)()(+) offer cylindrical pores that are occupied with the [Ru(III)Cl(6)](3)(-) anions. The presence of a C=N double bond of baia in 6 is judged from the C-N distance of 1.28(2) Å. It is suggested that the structural restraint enhanced by the attachment of alkylene chelates at the nitrogen donors of amines results in either the mislocation or misdirection of the donors, leading to the elongation of the Ru-N(amine) distances and to the weakening of their trans influence. Such structural strain is also discussed as related to the spectroscopic and electrochemical properties of the cis-[Ru(II)L(4)(bpy)](2+) complexes (L(4) = (NH(3))(4), (ethylenediamine)(2), and cyclam).

Journal Article↗
PubMed2006

A redox-active two-dimensional coordination polymer: preparation of silver and gold nanoparticles and crystal dynamics on guest removal.

A two-dimensional (2D) square-grid coordination polymer, {[Ni(cyclam)]2[BPTC]}n.2nH2O (1), has been assembled from [Ni(cyclam)](ClO4)2 (cyclam = 1,4,8,11-tetraazacyclotetradecane) and H4BPTC (H4BPTC = 1,1'-biphenyl-2,2',6,6'-tetracarboxylic acid) in H2O/MeOH (2.5:1, v/v) in the presence of triethylamine. When solid 1 was immersed in the EtOH solutions of AgNO3 (1.3 x 10(-1) M) and NaAuCl4.2H2O (3.4 x 10(-2) M), respectively, for 5 min at room temperature, solids including Ag (3.7 +/- 0.4 nm, diameter) and Au (2 nm, diameter) nanoparticles were formed by the redox reactions between Ni(II) ions incorporated in 1 and metal ions, as evidenced by HRTEM images, EPR, and XPS spectra. When single-crystal 1 was heated at 180 degrees C under 10(-5) Torr for 24 h, it was transformed to dehydrated compound {[Ni(cyclam)]2[BPTC]}n (2) in the single-crystal-to-single-crystal manner. The X-ray crystal structure of 2 reveals extensive dynamic motions of the molecular components in response to guest removal, involving rotation of the carboxylate and macrocycle, swing of the biphenyl, and bending of the macrocyclic coordination plane toward the carboxylate plane, which reduces the interlayer distance.

Journal Article↗
PubMed2006

Octahedral non-heme oxo and non-oxo Fe(IV) complexes: an experimental/theoretical comparison.

Electron-transfer series are described for three ferric complexes of the pentadentate ligand 4,8,11-trimethyl-1,4,8,11-tetraazacyclotetradecane-1-acetate (Me(3)cyclam-acetate) with axial chloride, fluoride, and azide ligands. These complexes can all be reduced coulometrically to their Fe(II) analogs and oxidized reversibly to the corresponding Fe(IV) species. The Fe(II), Fe(III), and Fe(IV) species have been studied spectroscopically and their UV-vis, Mössbauer, EPR, and IR spectra are presented. The fluoro species [(Me(3)cyclam-acetate)FeF](n+) (n = 0, 1, 2) have been studied computationally using density functional theory (DFT), and the electronic structure of the Fe(IV) dication [(Me(3)cyclam-acetate)FeF](2+) is compared with that of the isoelectronic Fe(IV) oxo cation [(Me(3)cyclam-acetate)FeO](+); the different properties of the two species are mainly due to the significantly covalent Fe=O pi bonds in the latter.

Acetates↗