The Dinitramide Anion, N(NO(2))(2)(-)

The infrared and Raman spectra of the NH(4)(+), K(+), and Cs(+) salts of N(NO(2))(2)(-) in the solid state and in solution have been measured and are assigned with the help of ab initio calculations at the HF/6-31G and MP2/6-31+G levels of theory. In agreement with the variations observed in the crystal structures, the vibrational spectra of the N(NO(2))(2)(-) anion are also strongly influenced by the counterions and the physical state. Whereas the ab initio calculations for the free N(NO(2))(2)(-) ion indicate a minimum energy structure of C(2) symmetry, Raman polarization measurements on solutions of the N(NO(2))(2)(-) anion suggest point group C(1) (i.e., no symmetry). This is attributed to the very small (<3 kcal/mol) N-NO(2) rotational barrier in N(NO(2))(2)(-) which allows for easy deformation.     

One-electron reduction of aqueous nitric oxide: a mechanistic revision

The pulse radiolysis of aqueous NO has been reinvestigated, the variances with the prior studies are discussed, and a mechanistic revision is suggested. Both the hydrated electron and the hydrogen atom reduce NO to yield the ground-state triplet (3)NO(-) and singlet (1)HNO, respectively, which further react with NO to produce the N(2)O(2)(-) radical, albeit with the very different specific rates, k((3)NO(-) + NO) = (3.0 +/- 0.8) x 10(9) and k((1)HNO + NO) = (5.8 +/- 0.2) x 10(6) M(-)(1) s(-)(1). These reactions occur much more rapidly than the spin-forbidden acid-base equilibration of (3)NO(-) and (1)HNO under all experimentally accessible conditions. As a result, (3)NO(-) and (1)HNO give rise to two reaction pathways that are well separated in time but lead to the same intermediates and products. The N(2)O(2)(-) radical extremely rapidly acquires another NO, k(N(2)O(2)(-) + NO) = (5.4 +/- 1.4) x 10(9) M(-)(1) s(-)(1), producing the closed-shell N(3)O(3)(-) anion, which unimolecularly decays to the final N(2)O + NO(2)(-) products with a rate constant of approximately 300 s(-)(1). Contrary to the previous belief, N(2)O(2)(-) is stable with respect to NO elimination, and so is N(3)O(3)(-). The optical spectra of all intermediates have also been reevaluated. The only intermediate whose spectrum can be cleanly observed in the pulse radiolysis experiments is the N(3)O(3)(-) anion (lambda(max) = 380 nm, epsilon(max) = 3.76 x 10(3) M(-)(1) cm(-)(1)). The spectra previously assigned to the NO(-) anion and to the N(2)O(2)(-) radical are due, in fact, to a mixture of species (mainly N(2)O(2)(-) and N(3)O(3)(-)) and to the N(3)O(3)(-) anion, respectively. Spectral and kinetic evidence suggests that the same reactions occur when (3)NO(-) and (1)HNO are generated by photolysis of the monoprotonated anion of Angeli's salt, HN(2)O(3)(-), in NO-containing solutions.     

Determination of N-NO bond dissociation energies of N-methyl-N-nitrosobenzenesulfonamides in acetonitrile and application in the mechanism analyses on NO transfer

The heterolytic and homolytic N-NO bond dissociation energies of seven substituted N-methyl-N-nitrosobenzenesulfonamides (abbreviated as G-MNBS, G = p-OCH(3), p-CH(3), p-H, p-Cl, p-Br, 2,5-2Cl, m-NO(2)) in acetonitrile solution were evaluated for the first time by using titration calorimetry and relative thermodynamic cycles according to Hess' law. The results show that the energetic scales of the heterolytic and homolytic N-NO bond dissociation energies of G-MNBS in acetonitrile solution cover the ranges from 44.3 to 49.5 and from 33.0 to 34.9 kcal/mol for the neutral G-MNBS, respectively, which indicates that N-methyl-N-nitrosobenzenesulfonamides are much easier to release a NO radical (NO(*)) than to release a NO cation (NO(+)). The estimation of the heterolytic and homolytic (N-NO)(-)(*) bond dissociation energies of the seven G-MNBS radical anions in acetonitrile solution gives the energetic ranges of -15.8 to -12.9 and -3.1 to 1.8 kcal/mol for the (N-NO)(-)(*) bond homolysis and heterolysis, respectively, which means that G-MNBS radical anions are very unstable at room temperature and able to spontaneously or easily release a NO radical or NO anion (NO(-)), but releasing a NO radical is easier than releasing NO anion. These determined N-NO bond dissociation energies of G-MNBS and their radical anions have been successfully used in the mechanism analyses of NO transfer from G-MNBS to 3,6-dibromocarbazole and the reactions of NO with the substituted N-methyl-benzenesulfonamide nitranions (G-MBSN(-)) in acetonitrile solution.     

Synthesis, characterization, and reactivity of [Ru(bpy)(CH3CN)3(NO2)]PF6, a synthon for [Ru(bpy)(L3)NO2] complexes

We report a high yield, two-step synthesis of fac-[Ru(bpy)(CH3CN)3NO2]PF6 from the known complex [(p-cym)Ru(bpy)Cl]PF6 (p-cym = eta(6)-p-cymene). [(p-cym)Ru(bpy)NO2]PF6 is prepared by reacting [(p-cymene)Ru(bpy)Cl]PF6 with AgNO3/KNO2 or AgNO2. The 15NO2 analogue is prepared using K15NO2. Displacement of p-cymene from [(p-cym)Ru(bpy)NO2]PF6 by acetonitrile gives [Ru(bpy)(CH3CN)3NO2]PF6. The new complexes [(p-cym)Ru(bpy)NO2]PF6 and fac-[Ru(bpy)(CH3CN)3NO2]PF6 have been fully characterized by 1H and 15N NMR, IR, elemental analysis, and single-crystal structure determination. Reaction of [Ru(bpy)(CH3CN)3NO2]PF6 with the appropriate ligands gives the new complexes [Ru(bpy)(Tp)NO2] (Tp = HB(pz)3-, pz = 1-pyrazolyl), [Ru(bpy)(Tpm)NO2]PF6 (Tpm = HC(pz)3), and the previously prepared [Ru(bpy)(trpy)NO2]PF6 (trpy = 2,2',6',2' '-terpyridine). Reaction of the nitro complexes with HPF6 gives the new nitrosyl complexes [Ru(bpy)TpNO][PF6]2 and [Ru(bpy)(Tpm)NO][PF6]3. All complexes were prepared with 15N-labeled nitro or nitrosyl groups. The nitro and nitrosyl complexes were characterized by 1H and 15N NMR and IR spectroscopy, elemental analysis, cyclic voltammetry, and single-crystal structure determination for [Ru(bpy)TpNO][PF6]2. For the nitro complexes, a linear correlation is observed between the nitro 15N NMR chemical shift and 1/nu(asym), where nu(asym) is the asymmetric stretching frequency of the nitro group.     

The elusive tetrasulfate anion [S4O13](2-)

Sulfates united: the unique tetrasulfate S(4)O(13)(2-) anion was observed in the structure of (NO(2))(2)[S(4)O(13)] that forms in the reaction of N(2)O(5) with SO(3). Theoretical investigations show that the anion is a stable member of the polysulfate series [S(n)O(3n+1)](2-), which was investigated up to n=11.     

Tuning the reactivity in classic low-spin d6 rhenium(I) tricarbonyl radiopharmaceutical synthon by selective bidentate ligand variation (L,L'-Bid; L,L'= N,N', N,O, and O,O' donor atom sets) in fac-[Re(CO)3(L,L'-Bid)(MeOH)]n complexes

A range of fac-[Re(CO)(3)(L,L'-Bid)(H(2)O)](n) (L,L'-Bid = neutral or monoanionic bidentate ligands with varied L,L' donor atoms, N,N', N,O, or O,O': 1,10-phenanthroline, 2,2'-bipydine, 2-picolinate, 2-quinolinate, 2,4-dipicolinate, 2,4-diquinolinate, tribromotropolonate, and hydroxyflavonate; n = 0, +1) has been synthesized and the aqua/methanol substitution has been investigated. The complexes were characterized by UV-vis, IR and NMR spectroscopy and X-ray crystallographic studies of the compounds fac-[Re(CO)(3)(Phen)(H(2)O)]NO(3)·0.5Phen, fac-[Re(CO)(3)(2,4-dQuinH)(H(2)O)]·H(2)O, fac-[Re(CO)(3)(2,4-dQuinH)Py]Py, and fac-[Re(CO)(3)(Flav)(CH(3)OH)]·CH(3)OH are reported. A four order-of-magnitude of activation for the methanol substitution is induced as manifested by the second order rate constants with (N,N'-Bid) < (N,O-Bid) < (O,O'-Bid). Forward and reverse rate and stability constants from slow and stopped-flow UV/vis measurements (k(1), M(-1) s(-1); k(-1), s(-1); K(1), M(-1)) for bromide anions as entering nucleophile are as follows: fac-[Re(CO)(3)(Phen)(MeOH)](+) (50 ± 3) × 10(-3), (5.9 ± 0.3) × 10(-4), 84 ± 7; fac-[Re(CO)(3)(2,4-dPicoH)(MeOH)] (15.7 ± 0.2) × 10(-3), (6.3 ± 0.8) × 10(-4), 25 ± 3; fac-[Re(CO)(3)(TropBr(3))(MeOH)] (7.06 ± 0.04) × 10(-2), (4 ± 1) × 10(-3), 18 ± 4; fac-[Re(CO)(3)(Flav)(MeOH)] 7.2 ± 0.3, 3.17 ± 0.09, 2.5 ± 2. Activation parameters (ΔH(k1)(++), kJmol(-1); ΔS(k1)(), J K(-1) mol(-1)) from Eyring plots for entering nucleophiles as indicated are as follows: fac-[Re(CO)(3)(Phen)(MeOH)](+) iodide 70 ± 1, -35 ± 3; fac-[Re(CO)(3)(2,4-dPico)(MeOH)] bromide 80.8 ± 6, -8 ± 2; fac-[Re(CO)(3)(Flav)(MeOH)] bromide 52 ± 5, -52 ± 15. A dissociative interchange mechanism is proposed.     

Chiral fluorous dialkoxy-diamino zirconium complexes: synthesis and use in stereospecific polymerization of 1-hexene

New catalysts for the isospecific polymerization of 1-hexene based on cationic zirconium complexes incorporating the tetradentate fluorous dialkoxy-diamino ligands [OC(CF(3))(2)CH(2)N(Me)(CH(2))(2)N(Me)CH(2)C(CF(3))(2)O](2-) [(ON(2)NO)(2-)] and [OC(CF(3))(2)CH(2)N(Me)(1R,2R-C(6)H(10))N(Me)CH(2)C(CF(3))(2)O](2-) [(ON(Cy)NO)(2-)] have been developed. The chiral fluorous diamino-diol [(ON(Cy)NO)H(2), 2] was prepared by ring-opening of the fluorinated oxirane (CF(3))(2)COCH(2) with (R,R)-N,N'-dimethyl-1,2-cyclohexanediamine. Proligand 2 reacts cleanly with [Zr(CH(2)Ph)(4)] and [Ti(OiPr)(4)] precursors to give the corresponding dialkoxy complexes [Zr(CH(2)Ph)(2)(ON(Cy)NO)] (3) and [Ti(OiPr)(2)(ON(Cy)NO)] (4), respectively. An X-ray diffraction study revealed that 3 crystallizes as a 1:1 mixture of two diastereomers (Lambda-3 and Delta-3), both of which adopt a distorted octahedral structure with trans-O, cis-N, and cis-CH(2)Ph ligands. The two diastereomers Lambda-3 and Delta-3 adopt a C(2)-symmetric structure in toluene solution, as established by NMR spectroscopy. Cationic complexes [Zr(CH(2)Ph)(ON(2)NO)(THF)(n)](+) (n=0, anion=[B(C(6)F(5))(4)](-), 5; n=1, anion=[PhCH(2)B(C(6)F(5))(3)](-), 6) and [Zr(CH(2)Ph)(ON(Cy)NO)(THF)](+)[PhCH(2)B(C(6)F(5))(3)](-) (7) were generated from the neutral parent precursors [Zr(CH(2)Ph)(2)(ON(2)NO)] (H) and [Zr(CH(2)Ph)(2)(ON(Cy)NO)] (3), and their possible structures were determined on the basis of (1)H, (19)F, and (13)C NMR spectroscopy and DFT methods. The neutral zirconium complexes H and 3 (Lambda-3/Delta-3 mixture), when activated with B(C(6)F(5))(3) or [Ph(3)C](+)[B(C(6)F(5))(4)](-), catalyze the polymerization of 1-hexene with overall activities of up to 4500 kg PH mol Zr(-1) h(-1), to yield isotactic-enriched (up to 74 % mmmm) polymers with low-to-moderate molecular weights (M(w)=4800-47 200) and monodisperse molecular-weight distributions (M(w)/M(n)=1.17-1.79).     

Pendant macrocyclic metallic building blocks for the design of cyano-bridged heterometallic complexes with 1D chain and 2D layer structures

A series of cyano-bridged Ni(II)-Cr(I/III) complexes have been synthesized by the reactions of hexaazacyclic Ni(II) complexes with [Cr(CN)(6)](3-) or [Cr(CN)(5)(NO)](3-). Using the tetravalent Ni(II) complex [Ni(H(2)L(2))](4+) (L(2) = 3,10-bis(2-aminoethyl)-1,3,6,8,10,12-hexaazacyclotetradecane), one-dimensional chainlike complexes were produced and subject to magnetic studies, affording the intermetallic magnetic exchange constants of J(1) = +0.23 cm(-1) and J(2) = +8.4 cm(-1) for the complex [Ni(H(2)L(2))][Cr(CN)(5)(NO)]ClO(4).5H(2)O (1) and of J = +5.9 cm(-1) for the complex [Ni(H(2)L(2))](4)[Cr(CN)(6)](5)OH.15H(2)O (2). X-ray diffraction analysis shows that complex 1 has a zigzag chain structure, whereas complex 2 consists of a branched chain structure. Complex 2 exhibits antiferromagnetic ordering at 8.0 K (T(N)). When an octahedral Ni(II) complex cis-[NiL(3)(en)](2+) (en = 1,2-ethylenediamine, L(3) = 3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane) was used for the synthesis, the common 2D honeycomb-layered complex [NiL(3)](3)[Cr(CN)(5)(NO)](2).8H(2)O (3) was obtained, which has a T(N) value of 3.3 K. Below T(N), a metamagnetic behavior was observed in complexes 2 and 3.     

Analysis of oxidizer salt mixtures by electrospray ionization mass spectrometry

Binary aqueous mixtures of NaNO3, KNO3 and NaClO4 oxidizers were analyzed using electrospray ionization mass spectrometry. Sodium nitrate solutions were observed to form doubly charged clusters of the type [(NaNO3)n2Na]2+ and [(NaNO3)n2NO3]2-, where n = 11, 13, 15, etc., in addition to singly charged cluster ions that have been reported previously. The identity of the doubly charged clusters was determined by tandem mass spectrometry. Two-component NaNO3-KNO3 salt solutions were observed to form cluster ions of the type [(NaNO3)i(KNO3)jNO3]- in the negative ion mode and [(NaNO3)i(KNO3)jNa]+ and [(NaNO3)i(KNO3)jK]+ in the positive ion mode, where i + j = 1, 2, 3 ... 10. Two-component solutions of KNO3-NaClO4 formed ions of the type [(KNO3)i(NaClO4)j(KClO4)k(NaNO3)lK](+) and [(KNO3)i(NaClO4)j(KClO4)k(NaNO3)lNa]+ in the positive ion mode, where i + j + k + l = 1, 2, 3 ... 10. Similar clusters containing excess nitrate and perchlorate to provide the charge are formed in the negative ion mode. In each case, the maximum number of spectral lines for a cluster of size n can be calculated as the number of combinations of n(th) order (where n = i + j) of N different cation-anion pairs taken with replication and without regard for the ordering of the N cation-anion pairs. The actual number of lines observed may be reduced due to degeneracy of nominal m/z values for some ions.     

Investigating chemical constraints to the measurement of phosphorus in soils using diffusive gradients in thin films (DGT) and resin methods

The effect of potential chemical constraints on the performance of two relatively new soil P testing methods, anion exchange membrane (AEM) and diffusive gradients in thin films (DGT), were evaluated. Exposures to ranges of anion (Cl(-), NO(3)(-), SO(4)(2-) and HCO(3)(-)) concentrations relevant to agricultural soils had minimal effect on P recoveries using DGT. It has also been shown previously that DGT P recoveries are unaffected by varying pH (3-9). In contrast, increasing NO(3)(-) and SO(4)(2-) concentrations in solution reduced the recovery of P using the resin method (anion exchange membrane, AEM) by 24% at 50mgL(-1) NO(3)(-) and by 47% at 12mgL(-1) SO(4)(2-) when the P concentration of the test solution was 2mgL(-1). Phosphorus sorption by the resin decreased with increasing Cl(-) concentrations until there was a 100% decrease at 300mgL(-1) Cl(-) when the P concentration of the test solution was 2mgL(-1) and a 92% reduction at 700mgL(-1) Cl(-) when the P concentration of the test solution was 0.2mgL(-1). There was also a small but significant effect of carbonate species on P sorption to the resin at carbonate concentrations that can occur in agricultural soils. Changing the pH of the solution had minimal effects on the resin P measurements in solutions above pH 4, but below pH 4, resin P measurements decreased dramatically. A poor coefficient of determination for the regression fit between DGT and resin measurements on eight agricultural soils suggested that these two methods are measuring different amounts of P for different soils. Resin P measurements increased significantly, but non-uniformly across soils, when the soil:water ratio was decreased but this did not result in an improved relationship with DGT P. There was a minimal effect on measured P using either Cl(-) or HCO(3)(-) as counter ions on the resin.     

Structural and mechanistic information on the nitrosation of model Fe(II) complexes containing a biomimetic S4N chelate

In order to provide insight into the reaction pathways of nitrogen oxide redox species with [Fe-S] models that may parallel those existing in biology, the reactivity of the iron-sulfur species, {[Fe(II)(S(4)NEt(2)N)]}(2) (1) and [Fe(II)(CH(3)CN)(S(4)NEt(2)N)] (2), where (S(4)NEt(2)N)(2-) = 2,6-bis(2-mercaptophenylthiomethyl)-4-diethylaminopyridine(2-), towards NO(+) (nitrosation) has been studied mechanistically in acetonitrile and compared with the corresponding reactions with NO (nitrosylation). For the nitrosation of 1, the reaction takes place in two steps that correspond to the nitrosation of the mononuclear (2) and dinuclear (1) complexes, respectively. For the corresponding carbonyl complex [Fe(II)(CO)(S(4)NEt(2)N)] (3), the nitrosation reaction occurs in a single step. The relative reactivity of the iron-sulfur species is approximately (1)/(2)/(3) = 1/20/10. Activation parameters for the nitrosation of 1 (ΔH(#) = 27 ± 1 kJ mol(-1), ΔS(#) = -111 ± 2 J K(-1) mol(-1), and ΔV(#) = -19 ± 2 cm(3) mol(-1)), 2 (ΔH(#) = 46 ± 2 kJ mol(-1), ΔS(#) = -22 ± 7 J K(-1) mol(-1), and ΔV(#) = -9.7 ± 0.4 cm(3) mol(-1)) and 3 (ΔH(#) = 38 ± 1 kJ mol(-1), ΔS(#) = -44 ± 4 J K(-1) mol(-1), and ΔV(#) = -7.8 ± 0.3 cm(3) mol(-1)) were determined from variable temperature and pressure studies. The significantly negative ΔS(#) and ΔV(#) values found for the nitrosation reactions are consistent with an associative mechanism. A comparative study of the reactivity of the iron-sulfur species 1 to 3 towards NO(+) and NO is presented.     

Realization of unusual ligand binding motifs in metalated container molecules: synthesis, structures, and magnetic properties of the complexes [(LMe)Ni2(mu-L')]n+ with L'=NO3-, NO2-, N3-, N2H4, pyridazine, phthalazine, pyrazolate, and benzoate

A series of dinickel(II) complexes with the 24-membered macrocyclic hexaazadithiophenol ligand H(2)L(Me) was prepared and examined. The doubly deprotonated form (L(Me))(2-) forms complexes of the type [(L(Me))Ni2II(mu-L')](n+) with a bioctahedral N(3)Ni(II)(mu-SR)(2)(mu-L')Ni(II)N(3) core and an overall calixarene-like structure. The bridging coordination site L' is accessible for a wide range of exogenous coligands. In this study L'=NO(3)(-), NO(2)(-), N(3)(-), N(2)H(4), pyrazolate (pz), pyridazine (pydz), phthalazine (phtz), and benzoate (OBz). Crystallographic studies reveal that each substrate binds in a distinct fashion to the [(L(Me))Ni(2)](2+) portion: NO(2)(-), N(2)H(4), pz, pydz, and phtz form mu(1,2)-bridges, whereas NO(3)(-), N(3)(-), and OBz(-) are mu(1,3)-bridging. These distinctive binding motifs and the fact that some of the coligands adopt unusual conformations is discussed in terms of complementary host-guest interactions and the size and form of the binding pocket of the [(L(Me))Ni(2)](2+) fragment. UV/Vis and electrochemical studies reveal that the solid-state structures are retained in the solution state. The relative stabilities of the complexes indicate that the [(L(Me))Ni(2)](2+) fragment binds anionic coligands preferentially over neutral ones and strong-field ligands over weak-field ligands. Secondary van der Waals interactions also contribute to the stability of the complexes. Intramolecular ferromagnetic exchange interactions are present in the nitrito-, pyridazine-, and the benzoato-bridged complexes where J=+6.7, +3.5, and +5.8 cm(-1) (H=-2 JS(1)S(2), S(1)=S(2)=1) as indicated by magnetic susceptibility data taken from 300 to 2 K. In contrast, the azido bridge in [(L(Me))Ni(2)(mu(1,3)-N(3))](+) results in an antiferromagnetic exchange interaction J=-46.7 cm(-1). An explanation for this difference is qualitatively discussed in terms of bonding differences.     

Layered copper hydroxide n-alkylsulfonate salts: synthesis, characterization, and magnetic behaviors in relation to the basal spacing

A series of hybrid inorganic-organic copper(II) hydroxy n-alkylsulfonate with a triangular lattice, Cu(2)(OH)(3)(C(n)H(2)(n)(+1)SO(3)) (n = 6, 8, 10), are prepared by anion exchange, starting from copper hydroxy nitrate Cu(2)(OH)(3)NO(3). These compounds show a layered structure as determined by X-ray diffraction, with interlayer distances of 14.3-34.8 A in alternation with interdigitated bilayer packing. Magnetic properties have been investigated by means of dc and ac measurements. All the compounds show similar metamagnet behaviors, with a Neel temperature of about 11 K. A subtle difference in the ac magnetic susceptibility among the compounds is understood by the existence of hydrogen bonding between the sulfonate headgroup and the hydroxide anion. A detailed molecular structure of the alkyl chains incorporated to the inorganic copper hydroxide layer is also discussed from the FTIR data.     

Metal Cyanide Ions Mx(CN)y]+,- in the gas phase: M = Fe,Co, Ni,Zn, Cd,Hg, Fe + Ag,Co + Ag

The generation of metal cyanide ions in the gas phase by laser ablation of M(CN)(2) (M = Co, Ni, Zn, Cd, Hg), Fe(III)[Fe(III)(CN)(6)] x xH(2)O, Ag(3)[M(CN)(6)] (M = Fe, Co), and Ag(2)[Fe(CN)(5)(NO)] has been investigated using Fourier transform ion cyclotron resonance mass spectrometry. Irradiation of Zn(CN)(2) and Cd(CN)(2) produced extensive series of anions, [Zn(n)(CN)(2n+1)](-) (1 < or = n < or = 27) and [Cd(n)(CN)(2n+1)](-) (n = 1, 2, 8-27, and possibly 29, 30). Cations Hg(CN)(+) and [Hg(2)(CN)(x)](+) (x = 1-3), and anions [Hg(CN)(x)](-) (x = 2, 3), are produced from Hg(CN)(2). Irradiation of Fe(III)[Fe(III)(CN)(6)] x xH(2)O gives the anions [Fe(CN)(2)](-), [Fe(CN)(3)](-), [Fe(2)(CN)(3)](-), [Fe(2)(CN)(4)](-), and [Fe(2)(CN)(5)](-). When Ag(3)[Fe(CN)(6)] is ablated, [AgFe(CN)(4)](-) and [Ag(2)Fe(CN)(5)](-) are observed together with homoleptic anions of Fe and Ag. The additional heterometallic complexes [AgFe(2)(CN)(6)](-), [AgFe(3)(CN)(8)](-), [Ag(2)Fe(2)(CN)(7)](-), and [Ag(3)Fe(CN)(6)](-) are observed on ablation of Ag(2)[Fe(CN)(5)(NO)]. Homoleptic anions [Co(n)(CN)(n+1)](-) (n = 1-3), [Co(n)(CN)(n+2)](-) (n = 1-3), [Co(2)(CN)(4)](-), and [Co(3)(CN)(5)](-) are formed when anhydrous Co(CN)(2) is the target. Ablation of Ag(3)[Co(CN)(6)] yields cations [Ag(n)(CN)(n-1)](+) (n = 1-4) and [Ag(n)Co(CN)(n)](+) (n = 1, 2) and anions [Ag(n)(CN)(n+1)](-) (n = 1-3), [Co(n)(CN)(n-1)](-) (n = 1, 2), [Ag(n)Co(CN)(n+2)](-) (n = 1, 2), and [Ag(n)Co(CN)(n+3)](-) (n = 0-2). The Ni(I) species [Ni(n)(CN)(n-1)](+) (n = 1-4) and [Ni(n)(CN)(n+1)](-) (n = 1-3) are produced when anhydrous Ni(CN)(2) is irradiated. In all cases, CN(-) and polyatomic carbon nitride ions C(x)N(y)(-) are formed concurrently. On the basis of density functional calculations, probable structures are proposed for most of the newly observed species. General structural features are low coordination numbers, regular trigonal coordination stereochemistry for d(10) metals but distorted trigonal stereochemistry for transition metals, the occurrence of M-CN-M and M(-CN-)(2)M bridges, addition of AgCN to terminal CN ligands, and the occurrence of high spin ground states for linear [M(n)(CN)(n+1)](-) complexes of Co and Ni.     

Dinuclear copper(II) complexes with {Cu2(mu-hydroxo)bis(mu-carboxylato)}+ cores and their reactions with sugar phosphate esters: A substrate binding model of fructose-1,6-bisphosphatase

Reactions of CuX2.nH2O with the biscarboxylate ligand XDK (H2XDK = m-xylenediamine bis(Kemp's triacid imide)) in the presence of N-donor auxiliary ligands yielded a series of dicopper(II) complexes, [Cu2(mu-OH)(XDK)(L)2]X (L = N,N,N',N'-tetramethylethylenediamine (tetmen), X = NO3 (1a), Cl (1b); L = N,N,N'-trimethylethylenediamine (tmen), X = NO3 (2a), Cl (2b); L =2,2'-bipyridine (bpy), X = NO3 (3); L = 1,10-phenanthroline (phen), X = NO3 (4); L = 4,4'-dimethyl-2,2'-bipyridine (Me2bpy), X = NO3 (5); L = 4-methyl-1,10-phenanthroline (Mephen), X = NO3 (6)). Complexes 1-6 were characterized by X-ray crystallography (Cu...Cu = 3.1624(6)-3.2910(4) A), and the electrochemical and magnetic properties were also examined. Complexes 3 and 4 readily reacted with diphenyl phosphoric acid (HDPP) or bis(4-nitrophenyl) phosphoric acid (HBNPP) to give [Cu2(mu-phosphate)(XDK)(L)2]NO3 (L = bpy, phosphate = DPP (11); L = phen, phosphate = DPP (12), BNPP (13)), where the phsophate diester bridges the two copper ions in a mu-1,3-O,O' bidentate fashion (Cu...Cu = 4.268(3)-4.315(1) A). Complexes 4 and 6 with phen and Mephen have proven to be good precursors to accommodate a series of sugar monophosphate esters (Sugar-P) onto the biscarboxylate-bridged dicopper centers, yielding [Cu2(mu-Sugar-P)(XDK)(L)2] (Sugar-P = alpha-D-Glc-1-P (23a and b), D-Glc-6-P (24a and b), D-Man-6-P (25a), D-Fru-6-P (26a and b); L = phen (a), Mephen (b)) and [Cu2(mu-Gly-n-P)(XDK)(Mephen)2] (Gly-n-P = glycerol n-phosphate; n = 2 (21), 3 (22)), where Glc, Man, and Fru are glucose, mannose, and fructose, respectively. The structure of [Cu2(mu-MNPP)(XDK)(phen)2(CH3OH)] (20) was characterized as a reference compound (H2MNPP = 4-nitrophenyl phosphoric acid). Complexes 4 and 6 also reacted with d-fructose 1,6-bisphosphate (D-Fru-1,6-P2) to afford the tetranuclear copper(II) complexes formulated as [Cu4(mu-D-Fru-1,6-P2)(XDK)2(L)4] (L = phen (27a), Mephen (27b)). The detailed structure of 27a was determined by X-ray crystallography to involve two different tetranuclear complexes with alpha- and beta-anomers of D-Fru-1,6-P2, [Cu4(mu-alpha-D-Fru-1,6-P2)(XDK)2(phen)4] and [Cu4(mu-beta-D-Fru-1,6-P2)(XDK)2(phen)4], in which the D-Fru-1,6-P2 tetravalent anion bridges the two [Cu2(XDK)(phen)2]2+ units through the C1 and C6 phosphate groups in a mu-1,3-O,O' bidentate fashion (Cu...Cu = 4.042(2)-4.100(2) A). Notably, the structure with alpha-D-Fru-1,6-P2 demonstrated the presence of a strong hydrogen bond between the C2 hydroxyl group and the C1 phosphate oxygen atom, which may support the previously proposed catalytic mechanism in the active site of fructose-1,6-bisphosphatase.     

Synthesis,Crystal Structure and Magnetic Properties of a Novel Copper Inverse-9-metallacrown-3 Complex

<正>The reaction of phenyl 2-pyridyl ketoxime(PhPyCNOH)with Cu(NO_3)_2·3H_2O has led to a triangular complex Cu_3(OH)(PhPyCNO)_3(NO_3)·NO_3·H_2O 1 containing the[Cu_3(μ_2-OH)]~(5+) core and possessing the very rare inverse 9-metallacrown-3 motif created by the bridging oximate groups.Crystallographic data for 1:C_(36_H_(30)N_8O_(11)Cu_3,M_r=941.30,monoclinic,space group C2/c,a =18.815(9),b=33.888(15),c=14.307(7)(?),β=118.945(6)°,V=7983(6)(?)~3,Z=8,D_c=1.566 g/cm~3,n=1.652 mm~(-1),F(000)= 3816,R= 0.0644 and wR= 0.1393 for 3468 observed reflections(I2σ(I)).Preliminary variable-temperature magnetic susceptibility studies reveal an antiferroma-gnetically -coupled system showing antisymmetric exchange.     

Halide and nitrite recognizing hexanuclear metallacycle copper(II) pyrazolates

Halide-centered hexanuclear, anionic copper(II) pyrazolate complexes [trans-Cu(6)((3,5-CF(3))(2)pz)(6)(OH)(6)X](-), X = Cl, Br, I are isolated in a good yield from the redox reaction of the trinuclear copper(I) pyrazolate complex [μ-Cu(3)((3,5-CF(3))(2)pz)(3)] with a halide source such as PPh(3)AuCl or [Bu(4)N]X, X = Cl, Br, or I, in air. X-ray structures of the anion-centered hexanuclear complexes show that the six copper atoms are bridged by bis(3,5-trifluoromethyl)pyrazolate and hydroxyl ligands above and below the six copper atom plane. The anions are located at the center of the cavity and weakly bound to the six copper atoms in a μ(6)-arrangement, Cu-X = ~3.1 ?. A nitrite-centered hexanuclear copper(II) pyrazolate complex [trans-Cu(6)((3,5-CF(3))(2)pz)(6)(OH)(6)(NO(2))](-) was obtained when a solution of [PPN]NO(2) in CH(3)CN was added dropwise to the trinuclear copper(I) pyrazolate complex [μ-Cu(3)((3,5-CF(3))(2)pz)(3)] dissolved in CH(3)CN, in air. Blue crystals are produced by slow evaporation of the acetonitrile solvent. The X-ray structure of [PPN][trans-Cu(6)((3,5-CF(3))(2)pz)(6)(OH)(6)(NO(2))] complex shows the nitrite anion sits in the hexanuclear cavity and is perpendicular to the copper plane with a O-N-O angle of 118.3(7)°. The (19)F and (1)H NMR of the pyrazolate ring atoms are sensitive to the anion present in the ring. Anion exchange of the NO(2)(-) by Cl(-) can be observed easily by (1)H NMR.     

Using delta15N and delta18O to evaluate the sources and pathways of NO3- in rainfall event discharge from drained agricultural grassland lysimeters at high temporal resolutions

The origin of NO(3) (-) yielded in drainage from agricultural grasslands is of environmental significance and has three potential sources; (i) soil organic mater (SOM), (ii) recent agricultural amendments, and (iii) atmospheric inputs. The variation in delta(15)N-NO(3) (-) and delta(18)O-NO(3) (-) was measured from the 'inter-flow' and 'drain-flow' of two 1 ha drained lysimeter plots, one of which had received an application of 21 m(3) of NH(4) (+)-N-rich agricultural slurry, during two rainfall events. Drainage started to occur 1 month after the application of slurry. The concentrations of NO(3) (-)-N from the two lysimeters were comparable; an initial flush of NO(3) (-)-N occurred at the onset of drainage from both lysimeters before levels quickly dropped to <1 mg NO(3) (-)-N L(-1). The isotopic signature of the delta(15)N-NO(3) (-) and delta(18)O-NO(3) (-) during the first two rainfall events showed a great deal of variation over short time-periods from both lysimeters. Isotopic variation of delta(15)N-NO(3) (-) during rainfall events ranged between -1.6 to +5.2 per thousand and +0.4 to +11.1 per thousand from the inter-flow and drain-flow, respectively. Variation in the delta(18)O-NO(3) (-) ranged from +2.0 to +7.8 per thousand and from +3.3 to +8.4 per thousand. No significant relationships between the delta(15)N-NO(3) (-) or delta(18)O-NO(3) (-) and flow rate were observed in most cases although delta(18)O-NO(3) (-) values indicated a positive relationship and delta(15)N-NO(3) (-) values a negative relationship with flow during event 2. Data from a bulked rainfall sample when compared with the theoretical delta(18)O-NO(3) (-) for soil microbial NO(3) (-) indicated that the contribution of rainfall NO(3) (-) accounted for 8% of the NO(3) (-) in the lysimeter drainage at most. The calculated contribution of rainfall NO(3) (-) was not enough to account for the depletion in delta(15)N-NO(3) (-) values observed during the duration of the rainfall event 2. The relationship between delta(15)N-NO(3) (-) and delta(18)O-NO(3) (-) from the drain-flow indicated that denitrification was causing enrichment in the isotopes from this pathway. The presence of slurry seemed to cause a relative depletion in delta(18)O-NO(3) (-) in the inter-flow and delta(15)N-NO(3) (-) in the drain-flow compared with the zero-slurry lysimeter. This may have been caused by increased microbial nitrification stimulated by the presence of increased NH(4) (+)-N.     

Mammalian DNA δ15N exhibits 40‰ intramolecular variation and is unresponsive to dietary protein level

We report the first high‐precision characterization of molecular and intramolecular δ¹⁵N of nucleosides derived from mammalian DNA. The influence of dietary protein level on brain amino acids and deoxyribonucleosides was determined to investigate whether high protein turnover would alter amino acid ¹⁵ N or ¹³ C values. Pregnant guinea pig dams were fed control diets, or high or low levels of dietary protein throughout gestation, and all pups were fed control diets. The cerebellar DNA of offspring was extracted at 2 and 120 days of life, nucleosides isolated and δ¹⁵N and δ¹³C values characterized. Mean diet δ¹⁵N was 0.45 ± 0.33‰, compared with cerebellar whole tissue and DNA δ¹⁵N = +4.1 ± 0.7‰ and ?4.5 ± 0.4‰, respectively. Cerebellar deoxythymidine (dT), deoxycytidine (dC), deoxyadenosine (dA), and deoxyguanosine (dG) δ¹⁵N were +1.4 ± 0.4, –2.1 ± 0.9, –7.2 ± 0.3, and ?10.4 ± 0.5‰, respectively. There were no changes in amino acid or deoxyribonucleoside δ¹⁵N values due to dietary protein level. Using known metabolic relationships, we developed equations to calculate the intramolecular δ¹⁵N values originating from aspartate (asp) in purines (pur) or pyrimidines (pyr), glutamine (glu), and glycine (gly) to be δ¹⁵N_ASP‐PUR, δ¹⁵N_ASP‐PYR, δ¹⁵N_GLN, and δ¹⁵N_GLY +11.9 ± 2.3‰, +7.0 ± 2.0‰, –9.1 ± 2.4‰, and ?31.8 ± 8.9‰, respectively. A subset of twelve amino acids from food and brain had mean δ¹⁵N values of 4.3 ± 3.2‰ and 13.8 ± 3.1‰, respectively, and δ¹⁵N values for gly and asp were 12.6 ± 2.2‰ and 15.2 ± 0.8‰, respectively. A separate isotope tracer study detected no significant turnover of cerebellar DNA in the first six months of life. The large negative δ¹⁵N difference between gly and cerebellar purine N at the gly (7) position implies either that there is a major isotope effect during DNA synthesis, or that in utero gly has a different isotope ratio during rapid growth and metabolism from that in adult life. Our data show that cerebellar nucleoside intramolecular δ¹⁵N values vary over more than 40‰ and are not influenced by dietary protein level or age. Copyright © 2011 John Wiley & Sons, Ltd.     

X-ray crystal structures, electron paramagnetic resonance, and magnetic studies on strongly antiferromagnetically coupled mixed mu-hydroxide-mu-N(1),N(2)-triazole-bridged one dimensional linear chain copper(II) complexes

Four new metal-organic polymeric complexes, {[Cu(mu-OH)(mu-ClPhtrz)][(H 2O)(BF 4)]} n ( 1), {[Cu(mu-OH)(mu-BrPhtrz)][(H 2O)(BF 4)]} n ( 2), {[Cu(mu-OH)(mu-ClPhtrz)(H 2O)](NO 3)} n ( 3), and {[Cu(mu-OH)(mu-BrPhtrz)(H 2O)](NO 3)} n ( 4) (ClPhtrz = N-[( E)-(4-chlorophenyl)methylidene]-4 H-1,2,4-triazol-4-amine; BrPhtrz = N-[( E)-(4-bromophenyl)methylidene]-4 H-1,2,4-triazol-4-amine), were synthesized in a reaction of substituted 1,2,4-triazole and various copper(II) salts in water/acetonitrile solutions. The structures of 1- 4 were characterized by single-crystal X-ray diffraction analysis. The Cu(II) ions are linked both by single N (1), N (2)-1,2,4-triazole and hydroxide bridges yielding one dimensional (1D) linear chain polymers. The tetragonally distorted octahedral geometry of copper atoms is completed alternately by two water and two BF 4 (-) anion molecules in 1 and 2 but solely by two water molecules in 3 and 4. Magnetic properties of all complexes were studied by variable temperature magnetic susceptibility measurements. The Cu(II) ions are strongly antiferromagnetically coupled with J = -419(1) cm (-1) ( 1), -412(2) cm (-1) ( 2), -391(3) cm (-1) ( 3), and -608(2) cm (-1) ( 4) (based on the Hamiltonian H = - J[ summation operator S i . S i+ 1]). The nature and the magnitude of the antiferromagnetic exchange were discussed on the basis of complementarity/countercomplementarity of the two competing bridges.