Ligand effects in cis-Ru-II(N-N)(2)L-2 species where N-N is a substituted 2,2 '-bisoxazoline and L is monodentate

Starting from previously reported cis-Ru(MeL)(2)Cl-2, where MeL is 4,4,4',4'-tetramethyl-2,2'-bisoxazoline, cis-Ru(MeL)(2)Br-2 (1), cis-Ru( MeL)(2)I-2 (2), cis-Ru(MeL)(2)(NCS)(2) center dot H2O (3), cis-Ru(MeL)(2)(N-3)(2) (4) and cis-[Ru(MeL)(2)(MeCN)(2)](PF6)(2) center dot (CH3)(2)CO (5) are synthesised. The X-ray crystal structures of complexes 1, 2, 3 and 5 have been determined. All the five new complexes have been characterized by FTIR, ESIMS and H-1 NMR. In cyclic voltammetry in acetonitrile at a glassy carbon electrode, the complexes display a quasireversible Ru(II/III) couple in the range 0.32-1.71 V versus NHE. The Ru(II/III) potentials yield a satisfactorily linear correlation with Chatt's ligand constants P-L for the monodantate ligands. From the intercept and by comparing the known situation in Ru(2,2'-bipyridine)(2)L-2, it is concluded that MeL, a non-aromatic diimine, is significantly more pi-acidic than 2,2'-bipyridine. (c) 2008 Elsevier B.V. All rights reserved.

Equilibrium studies on mixed ligand complex formation of Co(II), Ni(II), Cu(II) and Zn(II) with N-(2-hydroxybenzyl)-L-histidine (H(2)hb-L-his) and typical N,N donor ligands: Crystal structure of [Ni(hb-L-his)(bipyridine)]center dot H2O complex

Equilibrium study on complex formation of Co(II), Ni(II), Cu(II) and Zn(II), hereafter M(II), with the quadridentate (O-, N, O-, N) donor ligand, N-(2-hydroxybenzyl)-L-histidine (H(2)hb-L-his, hereafter H2L), in the absence and in the presence of typical (N, N) donor bidentate ligands, 1,10 phenanthroline(phen), 2, 2'-bipyridine(bipy), ethylenediamine(en), hereafter B, in aqueous solution at 25 +/- 1 degrees C was done at a fixed ionic strength, I = 0.1 mol dm(-3) (NaNO3) by combined pH-metric, UV-Vis and EPR measurements provide evidence for the formation of mononuclear and dinuclear binary and mixed ligand complexes of the types: M(L), M(L)(2)(2-), M-2(L)(2+), M-2(H-1L)(+), M(L)(B), (B)M(H-1L)M(B)(+). The imidazole moiety of the ligand is found to act as a bridging bidentate ligand in the dinuclear M-2(L)(2+), M-2(H-1L)(+) and (B)M(H-1L)M(B)(+) complexes, using its N-3 atom and N1-H deprotonated moiety. Stability constants of the complexes provide evidence of discrimination of Cu(II) from the other M(II) ions by this ligand. Solid complexes: [Ni(L)(H2O)(2)] (1), [Cu(L)(H2O)] (2), and [Ni(L)(bipy)] (.) H2O (3) have been isolated and characterized by various physicochemical studies. Single crystal X-ray diffraction of the ternary complex, 3, shows an octahedral [(O-,N,N,O-)(N,N)] geometry with extensive pi-pi stacking of the aromatic rings and H-bonding with imidazole (N1-H), secondary amino N-atom, the lattice H2O molecule, and the carboxylate and phenolate O-atoms. (c) 2006 Elsevier B.V. All rights reserved.

The representation of conditional expectations of non-Gaussian noise

For Wiener spaces conditional expectations and $L^{2}$-martingales w.r.t. the natural filtration have a natural representation in terms of chaos expansion. In this note an extension to larger classes of processes is discussed. In particular, it is pointed out that orthogonality of the chaos expansion is not required.

Zinc(II) mediated synthesis of an N-substituted 2-(2-pyridyl)imidazole from a 1,2-diketone and 2-(aminomethyl)pyridine and its ligational behaviour

Reaction of anhydrous ZnCl2 with the 1:2 condensate (L) of benzil and 2-(aminomethyl)pyridine in methanol gives monomeric ZnL'Cl-2 (1) where L' is 2-[(4,5-diphenyl-2-pyridin-2-yl-1H-imidazol-1-yl)-methyl]pyridine. In the X-ray crystal structure, 1 is found to contain tetrahedral zinc with an N2Cl2 coordination sphere and the N-substituent methylpyridine fragment hanging as a free arm. A tentative mechanism is proposed for the zinc mediated conversion of L-->L'. Demetallation of 1 by the action of aqueous NaOH yields L' in the free state. When L' is reacted with Zn(ClO4)(2).6H(2)O in a 1:2 molar proportion, [Zn(L')(2)](n)(ClO4)(2n).(H2O)(n/2).(CH2Cl2)(n/2) (2) is obtained. The zinc atom in 2, as revealed by X-ray crystallography, has a trigonal bipyramidal N-5 coordination sphere. There are two independent ligands in the asymmetric unit of 2. One of them bonds only to one zinc atom in a bidentate mode with the N-substituent methylpyridine hanging free while the other ligand binds to two different zinc atoms in a tridentate fashion, employing the N-substituent methylpyridine nitrogen atom to form the polymeric one-dimensional chain cation.

Extraction and coordination studies of the unexplored bifunctional ligand carbamoyl methyl sulfoxide (CMSO) with uranium(VI) and cerium(III) nitrates. Synthesis and structures of [UO2(NO3)(2)((PhSOCH2CONBu2)-Bu-i)] and [Ce(NO3)(3)(PhSOCH2CONBu2)(2)]

The bifunctional carbamoyl methyl sulfoxide ligands, PhCH2SOCH2CONHPh (L-1), PhCH2SOCH2CONHCH2Ph (L-2), (PhSOCH2CONPr2)-Pr-i (L-3), PhSOCH2CONBu2 (L-4), (PhSOCH2CONBu2)-Bu-i (L-5) and PhSOCH2CON(C8H17)(2) (L-6) have been synthesized and characterized by spectroscopic methods. The selected coordination chemistry of L-1, L-3, L-4 and L-5 with [UO2(NO3)(2)] and [Ce(NO3)(3)] has been evaluated. The structures of the compounds [UO2(NO3)(2)((PhSOCH2CONBu2)-Bu-i)] (10) and [Ce(NO3)(3)(PhSOCH2CONBu2)(2)] (12) have been determined by single crystal X-ray diffraction methods. Preliminary extraction studies of ligand L-6 with U(VI), Pu(IV) and Am(III) in tracer level showed an appreciable extraction for U(VI) and Pu(IV) in up to 10 M HNO3 but not for Am(III). Thermal studies on compounds 8 and 10 in air revealed that the ligands can be destroyed completely on incineration. The electron spray mass spectra of compounds 8 and 10 in acetone show that extensive ligand distribution reactions occur in solution to give a mixture of products with ligand to metal ratios of 1 : 1 and 2 : 1. However, 10 retains its solid state structure in CH2Cl2.

(Ni-2), (Ni-3), and (Ni-2 + Ni-3): A Unique Example of Isolated and Cocrystallized Ni-2 and Ni-3 Complexes

Structural and magnetic characterization of compound {[Ni-2(L)(2)(OAC)(2)][Ni-3(L)(2) (OAc)(4)]) center dot 2CH(3)CN (3) (HL = the tridentate Schiff base ligand, 2-[(3-methylaminb-propylimino)-methyl]-phenol) shows that it is a rare example of a crystal incorporating a dinuclear Ni(II) compound, [Ni-2(L)(2)(OAc)(2)], and a trinuclear one, [Ni-3(L)(2)(OAC)(4)]. Even more unusual is the fact that both Ni (II) complexes, [Ni-2(L)(2)(OAc)(2)] (1) and [Ni-3(L)(2)(OAc)(4)(H2O)(2)] center dot CH2Cl2 center dot 2CH(3)OH (2), have also been isolated and structurally and magnetically characterized. The structural analysis reveals that the dimeric complexes [Ni-2(L)(2)(OAc)(2)] in cocrystal 3 and in compound 1 are almost identical-in both complexes, the Ni(II) ions possess a distorted octahedral geometry formed by the chelating tridentate ligand (L), a chelating acetate ion, and a bridging phenoxo group with very similar bond angles and distances. On the other hand, compound 2 and the trinuclear complex in the cocrystal 3 show a similar linear centrosymmetric structure with the tridentate ligand coordinated to the terminal Ni(II) and linked to the central Ni(II) by phenoxo and carboxylate bridges. The only difference is that a water molecule found in 2 is not present in the trinuclear unit of complex 3; instead, the coordination sphere is completed by an additional bridging oxygen atom from an acetate ligand. Variable-temperature (2-300 K) magnetic susceptibility measurements show that the dinuclear unit is antiferromagnetically coupled in both compounds (2J = -36.18 and -29.5 cm(-1) in 1 and 3, respectively), whereas the trinuclear unit shows a very weak ferromagnetic coupling in compound 3 (2J = 0.23 cm(-1)) and a weak antiferromagnetic coupling in 2 (2J = -8.7(2) cm(-1)) due to the minor changes in the coordination sphere.

Structural and spectroscopic properties of Ru(II) complexes of 4-(aryl)thiosemicarbazones of thiophen-2-carbaldehyde

Six Ru(II) complexes of formula [Ru(L)(2)(PPh3)(2)] have been prepared where LH = 4-(aryl)thiosemicarbazones of thiophen-2-carbaldehyde. X-ray crystal structures of five of the complexes are reported. In all the complexes ruthenium is six coordinate with a distorted octahedral cis-P-2, cis-N-2, trans-S-2 donor environment, and each of the two thiosemicarbazone ligands are coordinated in a bidentate fashion forming a four membered chelate ring. The complexes undergo a one-electron oxidation at similar to 0.5 V vs. Ag/AgCl. The EPR spectrum of the electrochemically oxidized solution at 100 K shows a rhombic signal, with transitions at g(1) = 2.27, g(2) = 2.00 and g(3) = 1.80. DFT calculations on one of the complexes suggest that there is 35% ruthenium and 17% sulfur orbital contribution to the HOMO. These results suggest that the assignment of metal atom oxidation states in these compounds is not unambiguous. (C) 2009 Elsevier Ltd. All rights reserved.

Different supramolecular hydrogen bond structures and significant changes in magnetic properties in dinuclear mu(2)-1,1-N-3 copper(II) complexes with very similar tridentate Schiff base blocking ligands

Three new basal-apical, mu(2)-1,1-azide bridged complexes, [CuL1(N-3)](2) (1), [CuL2(N-3)](2) (2) and [CuL3(N-3)]2 (3) with very similar tridentate Schiff base blocking ligands [L-1=N-(3-aminopropyl) salicylaldimine, L-2=7-amino-4-methyl-5-azahept-3-en-2-one and L-3=8-amino-4-methyl-5-azaoct-3-en-2-one) have been synthesised and their molecular structures determined by X-ray crystallography. In complex 1, there is no inter-dimer H-bonding. However, complexes 2 and 3 form two different supramolecular structures in which the dinuclear entities are linked by strong H-bonds giving one-dimensional systems. Variable-temperature (300-2 K) magnetic susceptibility measurements and magnetization measurements at 2 K reveal that complexes 1 and 2 have antiferromagnetic coupling while 3 has ferromagnetic coupling which is also confirmed by EPR spectra at 4-300 K. Magnetostructural correlations have been made taking into consideration both the azido bridging ligands and the existence of intermolecular hydrogen bonds in complexes 2 and 3.

Spectroscopic properties and electronic structures of 17-electron half-sandwich ruthenium acetylide complexes, [Ru(CCAr)(L2)Cp′]+ (Ar=phenyl, p-tolyl, 1-naphthyl, 9-anthryl; L2=(PPh3)2, Cp′=Cp; L2=dppe; Cp′=Cp∗)

A series of half-sandwich bis(phosphine) ruthenium acetylide complexes [Ru(C CAr)(L-2)Cp'] (Ar = phenyl, p-tolyl, 1-naphthyl, 9-anthryl; L2 = (PPh3)(2), Cp' = Cp; L-2 = dppe; Cp' = Cp*) have been examined using electrochemical and spectroelectrochemical methods. One-electron oxidation of these complexes gave the corresponding radical cations [Ru(C CAr)(L2)Cp'](+). Those cations based on Ru(dppe)Cp*, or which feature a para-tolyl acetylide substituent, are more chemically robust than examples featuring the Ru(PPh3)(2)Cp moiety, permitting good quality UV-Vis-NIR and IR spectroscopic data to be obtained using spectroelectrochemical methods. On the basis of TD DFT calculations, the low energy (NIR) absorption bands in the experimental electronic spectra for most of these radical cations are assigned to transitions between the beta-HOSO and beta-LUSO, both of which have appreciable metal d and ethynyl pi character. However, the large contribution from the anthryl moiety to the frontier orbitals of [Ru(C CC14H9)(L2)CP'](+) suggests compounds containing this moiety should be described as metal-stabilised anthryl radical cations.

A well-posed integral equation formulation for three-dimensional rough surface scattering

We consider the problem of scattering of time-harmonic acoustic waves by an unbounded sound-soft rough surface. Recently, a Brakhage Werner type integral equation formulation of this problem has been proposed, based on an ansatz as a combined single- and double-layer potential, but replacing the usual fundamental solution of the Helmholtz equation with an appropriate half-space Green's function. Moreover, it has been shown in the three-dimensional case that this integral equation is uniquely solvable in the space L-2 (Gamma) when the scattering surface G does not differ too much from a plane. In this paper, we show that this integral equation is uniquely solvable with no restriction on the surface elevation or slope. Moreover, we construct explicit bounds on the inverse of the associated boundary integral operator, as a function of the wave number, the parameter coupling the single- and double-layer potentials, and the maximum surface slope. These bounds show that the norm of the inverse operator is bounded uniformly in the wave number, kappa, for kappa > 0, if the coupling parameter h is chosen proportional to the wave number. In the case when G is a plane, we show that the choice eta = kappa/2 is nearly optimal in terms of minimizing the condition number.

Acoustic scattering by mildly rough unbounded surfaces in three dimensions

For a nonlocally perturbed half- space we consider the scattering of time-harmonic acoustic waves. A second kind boundary integral equation formulation is proposed for the sound-soft case, based on a standard ansatz as a combined single-and double-layer potential but replacing the usual fundamental solution of the Helmholtz equation with an appropriate half- space Green's function. Due to the unboundedness of the surface, the integral operators are noncompact. In contrast to the two-dimensional case, the integral operators are also strongly singular, due to the slow decay at infinity of the fundamental solution of the three-dimensional Helmholtz equation. In the case when the surface is sufficiently smooth ( Lyapunov) we show that the integral operators are nevertheless bounded as operators on L-2(Gamma) and on L-2(Gamma G) boolean AND BC(Gamma) and that the operators depend continuously in norm on the wave number and on G. We further show that for mild roughness, i.e., a surface G which does not differ too much from a plane, the boundary integral equation is uniquely solvable in the space L-2(Gamma) boolean AND BC(Gamma) and the scattering problem has a unique solution which satisfies a limiting absorption principle in the case of real wave number.

Effect of plasma insulin and branched-chain amino acids on skeletal muscle protein synthesis in fasted lambs

The increase in fractional rate of protein synthesis (K-s) in the skeletal muscle of growing rats during the transition from fasted to fed state has been explained by the synergistic action of a rise in plasma insulin and branched-chain amino acids (BCAA). Since growing lambs Also exhibit an increase in K-s with level of feed intake, the objective of the present study was to determine if this synergistic relationship between insulin and BCAA also occurs in ruminant animals. Six 30 kg fasted (72 h) lambs (8 months of age) received each of four treatments, which were based on continuous infusion into the jugular vein for 6 h of: (1) saline (155 mmol NaCl/l); (2) a mixture of BCAA (0.778 mumol leucine, 0.640 mumol isoleucine and 0.693 mumol valine/min.kg); (3) 18.7 mumol glucose/min.kg (to induce endogenous insulin secretion): (4) co-infusion of BCAA and glucose. Within each period all animals received the same isotope of phenylalanine, (Phe) as follows: (1) L-[1-C-13]Phe; (2) L-phenyl-[ring H-2(5)]-alanine; (3) L-[N-15]Phe; (4) L-[ring 2,6-H-3]Phe. Blood was sampled serially during infusions to measure plasma concentrations of insulin, glucose and amino acids, and plasma free Phe isotopic activity; biopsies were taken 6 h after the beginning of infusions to determine K-s in in. longissimus dorsi and vastus muscle. Compared with control (saline-infused) lambs, K-s was increased by an average of 40% at the end of glucose infusion, but this effect was not statistically significant in either of the muscles sampled. BCAA infusion, alone or in combination with glucose, also had no significant effect on K-s compared with control sheep. K-s was approximately 60% greater for vastus muscle than for m. longissimus dorsi (P<0.01), regardless of treatment. It is concluded that there are signals other than insulin and BCAA that are responsible for the feed-induced increase in K-s in muscle of growing ruminant animals.

Dinuclear complexes of M-II thiocyanate (M = Ni and Cu) containing a tridentate Schiff-base ligand: synthesis, structural diversity and magnetic properties

A dinuclear Ni-II complex, [Ni-2(L)(2)(H2O)(NCS)(2)]center dot 3H(2)O (1) in which the metal atoms are bridged by one water molecule and two mu(2)-phenolate ions, and a thiocyanato-bridged dimeric Cull complex, [Cu(L)NCS](2) (2) [L = tridentate Schiff-base ligand, N-(3-aminopropyl)salicylaldimine, derived from 1:1 condensation of salicylaldehyde and 1,3-diaminopropane], have been synthesized and characterized by IR and UV/Vis spectroscopy, cyclic voltammetry and single-crystal X-ray diffraction studies. The structure of 1 consists of dinuclear units with crystallographic C-2 symmetry in which each Ni-II atom is in a distorted octahedral environment. The Ni-O distance and the Ni-O-Ni angle, through the bridged water molecule, are 2.240(11) angstrom and 82.5(5)degrees, respectively. The structure of 2 consists of dinuclear units bridged asymmetrically by di-mu(1,3)-NCS ions; each Cull ion is in a square-pyramidal environment with tau = 0.25. Variable-temperature magnetic susceptibility studies indicate the presence of dominant ferromagnetic exchange coupling in complex 1 with J = 3.1 cm(-1), whereas complex 2 exhibits weak antiferromagnetic coupling between the Cu-II centers with J = -1.7 cm(-1). ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Stabilization of a helical water chain in a metal-organic host of a trinuclear Schiff base complex

Three heterometallic trinuclear Schiff base complexes, [{GuL(1)(H2O)}(2)Ni(CN)(4)]center dot 4H(2)O (1), [{CuL2(H2O)}(2)Ni(CN)(4)] (2), and [{CuL3(H2O)}(2)Ni(CN)(4)] (3) (HL1 = 7-amino-4-methyl-5-azahept-3-en-2-one, HL2 = 7-methylamino-4-methyl-5-azahept-3-en-2-one, and HL3 = 7-dimethylamino-4-methyl-5-azahept-3-en-2-one), were synthesized. All three complexes were characterized by elemental analysis, IR and UV spectroscopies, and thermal analysis. Two of them (1 and 3) were also characterized by single crystal X-ray crystallography. Complex 1 forms a hydrogen-bonded one-dimensional metal-organic framework that stabilizes a helical water chain into its cavity, but when any of the amine hydrogen atoms of the Schiff base are replaced by methyl groups, as in L 2 and L 3, the water chain, vanishes, showing explicitly the importance of the host-guest H-bonding interactions for the stabilization of a water cluster.

Nickel(II) complexes of terdentate or symmetrical tetradentate Schiff bases: Evidence of the influence of the counter anions in the hydrolysis of the imine bond in Schiff base complexes

Two sets of ligands, set-1 and set-2, have been prepared by mixing 1,3-diaminopentane and carbonyl compounds (2-acetylpyridine or pyridine-2-carboxaldehyde) in 1:1 and 1:2 ratios, respectively, and employed for the synthesis of complexes with Ni(II) perchlorate, Ni(II) thiocyanate and Ni(II) chloride. Ni(II) perchlorate yields the complexes having general formula [NiL2](ClO4)(2)(L = L-1 [N-3-(1-pyridin-2-yl-ethylidene)-pentane-1,3-diamine] for complex 1 or L-2[N-3-pyridin-2-ylmethylene-pentane-1,3-diamine] for complex 2) in which the Schiff bases are monocondensed terdentate, whereas Ni(II) thiocyanate results in the formation of tetradentate Schiff base complexes, [NiL(SCN)(2)] (L = L-3[N,N'-bis-(1-pyridin-2- yl-ethylidine)-pentane-1,3-diamine] for complex 3 or L-4 [N,N'-bis(pyridin-2-ylmethyline)-pentane-1,3- diamine] for complex 4) irrespective of the sets of ligands used. Complexes 5 {[NiL3(N-3)(2)]} and 6 {[NiL4(N-3)(2)]} are prepared by adding sodium azide to the methanol solution of complexes 1 and 2. Addition of Ni(II) chloride to the set-1 or set-2 ligands produces [Ni(pn)(2)]Cl-2, 7, as the major product, where pn = 1,3-diaminopentane. Formation of the complexes has been explained by the activation of the imine bond by the counter anion and thereby favouring the hydrolysis of the Schiff base. All the complexes have been characterized by elemental analyses and spectral data. Single crystal X-ray diffraction studies con. firm the structures of three representative members, 1, 4 and 7; all of them have distorted octahedral geometry around Ni(II). The bis-complex of terdentate ligands, 1, is the mer isomer, and complexes 4 and 7 possess trans geometry. (C) 2008 Elsevier B. V. All rights reserved.