Lanthanide metal complexes for the hydrolysis of adenosine-5'-monophosphate and deoxyadenosine-5'-monophosphate

The hydrolysis of adenosine-5'-monophosphate and deoxyadenosine-5'-monophosphate has been studied with lanthanide(III) metal complexes of 2-carboxyethylgermanium sesquioxide (Ge-132) by NMR and HPLC and by measuring the liberated inorganic phosphates.

Lanthanide metal complexes for the hydrolysis of ribonucleoside 3',5'-cyclic phosphate and deoxyribonucleoside 3',5'-cyclic phosphate

Ytterbium(III) and praseodymium(III) complexes of 2-carboxyethylgermanium sesquioxide (Ge-132) can hydrolyze the phosphodiester linkage of 3',5'-cyclic adenosine monophosphate (cAMP) and 3',5'-cyclic deoxyadenosine monophosphate (dcAMP). Both cAMP and dcAMP are hydrolyzed with high selectivity, yielding predominantly 3'-monophosphates. The selectivity and activity for hydrolyzing cAMP and dcAMP by lanthanide metal(III) complexes and lanthanide metal ions are compared.

Synthesis of lanthanide-alkylaluminium bimetallic complexes and studies on their catalytic activities for polymerization of some polar monomers

Three new lanthanide (Ln)-alkylaluminium (Al) bimetallic complexes with the formula [(mu-CF3CO2)(2)Ln(mu-CF3CHO2)AIR(2) . 2THF](2) (Ln = Nd, Y, R=i-C4H9 (i-Bu); Ln=Eu, R=C2H5(Et); THF=tetrahydrofuran) were synthesized by the reaction of Ln(CF,CO,), (Ln=Nd, Y) with HAI (i-Bu)(2) and of Eu(CF3CO2)(3) with AlEt(3), respectively. Their crystal structures were determined by X-ray diffraction at 233 K. [(mu-CF3CO2)(2)Nd (mu-CF3CHO2)Al(i-Bu)(2) . 2THF](2) (Nd-Al) and [(mu-CF3CO2)(2)Y(mu-CF3CHO2)Al(i-Bu)(2) . 2THF](2) (Y-Al) are isomorphous and crystallize in space group with a=12.441(3) Angstrom [12.347(5) Angstrom for Y-Al], b=12.832(3) Angstrom [12.832(4) Angstrom], c=11.334(3) Angstrom [11.292(8) Angstrom], alpha=104.93 (2)degrees [104.45(4)degrees], beta=98.47(2)degrees [98.81(4)degrees], gamma=64.60(2)degrees [64.30(3)degrees], R=0.519 [0.113], R(w)=0.0532 [0.110], Z=1 and [(mu-CF3CO2)(2)Eu(CF3CHO2)AlEt(2) . 2THF](2)(Eu-Al) in space group P2(1)/n with a=11.913(6) Angstrom, b=14.051(9) Angstrom, c=17.920(9) Angstrom, alpha=101.88(11)degrees, beta=gamma=90 degrees, R=0.0509, R(w)=0.0471 and Z=2. The six CF3CO2- (including CF3CHO2-) of each complex, among which pairs are equivalent, coordinated to Ln and Al in three patterns: (A) the two oxygen atoms in one of the three CF3CO2- type coordinated to two different Ln; (B) the two oxygen atoms in the second of CF3CO2- type coordinated to Ln and Al, respectively; (C) one of the two oxygen atoms in the third CF3CO2- type bidentately coordinated to two Ln and another oxygen coordinated to Al and one of the two Ln, respectively. Unlike types A and B, in type C the carboxyl carbon with a hydrogen atom bonded to it was found to appear as an sp(3)-hybridized configuration rather than an sp(2)-one. 1D and 2D NMR results further confirmed the existence of such a disproportionated CF3CHO2- ligand. Methyl methacrylate (MMA) and epichlorohydrin (ECH) could be polymerized by Y-Al or Eu-Al as a single-component catalyst and highly syndiotactic poly(MMA) was obtained. THF could also be polymerized by Y-Al in the presence of a small amount of ECH.

LANTHANIDE PERCHLORATE COMPLEXES OF 1,4-BIS(PHENYLSULFINYL)BUTANE

Seven trivalent lanthanide perchlorate complexes of the types [Ln(bphab)(4)ClO4] (ClO4)2 (where La = La(III), Pr(III), Nd(III) and Eu(III)) and [Ln(bphab)(3)ClO4] (ClO4)(2) (where Ln = Ho(III), Er(III) and Lu(III), and bphab = 1,4-bis(phenylsulfinyl)butane) have been synthesized by the reaction of bphsb with lanthanide(III) perchlorate in methanol-chloroform mixture. The complexes have been characterized by elemental analyses, molar conductance, electronic and infrared spectral techniques. Several bonding parameters have been calculated from the absorption spectra of the Pr(III), Nd(III), Ho(III) and Er(III) complexes. Infrared spectral data suggest that bphsb acts as bidentate ligand coordinating through the oxygen atoms of the S=O moieties.

SYNTHESIS AND CHARACTERIZATION OF HETEROPOLY BLUES OF BIS-2/17 MOLYBDOPHOSPHATE COMPLEXES WITH LANTHANIDE

Eight heteropoly blues of bis-2:17 molybdophosphate complexes with Lathanide, i.e., K17H2[Ln(P2Mo17O61)2] . nH2O and K17H4[Ln(P2Mo17O61)2] . nH2O were synthesized and characterized by elemental analyses potentiometric titration, IR, UV, polarography, cyclic voltammetry, X-ray photoelectron spectra X-ray powder diffraction, thermal analyses and ESR. Experimental results show that the properties of these series of heteropoly blues are different from those of their oxidized form, but no great changes in their structures were observed. The ligand P2Mo17O6110- remains alpha2-isomer's configuration.

SYNTHESES AND X-RAY STRUCTURES OF BIS(T-BUTYLCYCLOPENTADIENYL)LANTHANIDE CHLORIDE COMPLEXES [(BU(T)CP)2LNCL]2 (LN = PR, GD, ER)

Reaction of lanthanide trichlorides with two equivalents of sodium t-butylcyclopentadienide in THF gave rise to the bis(t-butylcyclopentadienyl)lanthanide chloride complexes [(Bu(t)Cp)2LnCl]2 (Ln = Pr, Gd, Er), which were characterized by elemental analysis, IR and H-1 NMR spectroscopy. In addition, the crystal structures of [(ButCp)2PrCl]2 (1) and [(ButCp)2GdCl]2 (2) were determined by single crystal X-ray diffraction at room temperature. The coordination number for Pr3+ and Gd3+ is 8 and the bond lengths Pr-Cl and Gd-Cl are 2.864(2) and 2.771(3) angstrom, respectively. The structural studies showed the complexes to have C2h symmetry.

Mandelohydroxamic acid as ligand for copper(II) 15-metallacrown-5 lanthanide(III) and copper(II) 15-metallacrown-5 uranyl complexes

The formation of pentanuclear copper(ii) complexes with the mandelohydroxamic ligand was studied in solution by electrospray ionization mass spectrometry (ESI-MS), absorption spectrophotometry, circular dichroism and H-1 NMR spectroscopy. The presence of lanthanide(iii) or uranyl ions is essential for the self-assembly of the 15-metallacrown-5 compounds. The negative mode ESI-MS spectra of solutions containing copper(II), mandelohydroxamic acid and lanthanide(iii) ions (Ln = La, Ce, Nd, Eu, Gd, Dy, Er, Tm, Lu, Y) or uranyl in the ratio 5:5:1 showed only the peaks that could be unambiguously assigned to the following intact molecular ions: {Ln(NO3)(2)[15-MCuIIN(MHA)-5](2-)}(-) and {Ln(NO3)[15-MCCuIIN(MHA)-5](3-)}(-), where MHA represents doubly deprotonated mandelohydroxamic acid. The NMR spectra of the pentanuclear species revealed only one set of peaks indicating a fivefold symmetry of the complex. The pentanuclear complexes synthesized with the enantiomerically pure R- or S-forms of mandelohydroxamic acid ligand, showed circular dichroism spectra which were mirror images of each other. The pentanuclear complex made from the racemic form of the ligand showed no signals in the CD spectrum. The UV/ Vis titration experiments revealed that the order in which the metal salts are added to the solution of the mandelohydroxamic acid ligand is crucial for the formation of metallacrown complexes. The addition of copper(ii) to the solutions containing mandelohydroxamic acid and neodymium(iii) in a 5:1 ratio lead to the formation of a pentanuclear complex in solution. In contrary, titration of lanthanide(iii) salt to the solution containing copper(ii) and mandelohydroxamic acid did not show any evidence for the formation of pentanuclear species. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Synthesis, structure, and redox states of homoleptic d-block metal complexes with bis-1,2,4-triazin-3-yl-pyridine and 1,2,4-triazin-3-yl-bipyridine extractants

it has been established that triazinyl bipyridines (hemi-BTPs) and bis-triazinyl pyridines (BTPs), ligands which are currently being investigated as possible ligands for the separation of actinides from lanthanides in nuclear waste, are able to form homoleptic complexes with first row transition metals such as cobalt(IT), copper(II), iron(II), manganese(II), nickel(II) and zinc(II). The metal complexes exhibit six-co-ordinate octahedral structures and redox states largely analogous to those of the related terpyridine complexes. The reactivity of the different redox states of cobalt bis-hemi-BTP complex in aqueous environments has been studied with two-phase electrochemistry by immobilisation of the essentially water-insoluble metal complexes on graphite electrodes and the immersion of this modified electrode in an aqueous electrolyte. It was found that redox potentials for the metal-centred reactions were pH-independent whereas the potentials for the ligand-centred reactions were strongly pH-dependent. The reductive degradation of these complexes has been investigated by computational methods. Solvent extraction experiments have been carried out for a range of metals and these show that cobalt(II) and nickel(II) as well as palladium(II), cadmium(II) and lead(II) were all extracted with the ligands 1e and 2c with higher distribution ratios that was observed for americium(III) under the same conditions. The implications of this result for the use of these ligands to separate actinides from nuclear waste are discussed. (c) 2005 Elsevier Ltd. All rights reserved.

Homoleptic copper(II) and copper(I) complexes of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline. Six-coordinate copper(I) in solution

Reaction of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline (L) with Cu(ClO(4))(2)center dot 6H(2)O in methanol in 3:1 M ratio at room temperature yields light green [CuL(3)](ClO(4))(2)center dot H(2)O (1). The X-ray crystal structure of the hemi acetonitrile solvate [CuL(3)](ClO(4))(2)center dot 0.5CH(3)CN has been determined which shows Jahn-Teller distortion in the CuN(6) core present in the cation [CuL(3)](2+). Complex 1 gives an axial EPR spectrum in acetonitrile-toluene glass with g(parallel to) = 2.262 (A(parallel to) = 169 x 10 (4) cm (1)) and g(perpendicular to) = 2.069. The Cu(II/I) potential in 1 in CH(2)Cl(2) at a glassy carbon electrode is 0.32 V versus NHE. This potential does not change with the addition of extra L in the medium implicating generation of a six-coordinate copper(I) species [CuL(3)](+) in solution. B3LYP/LanL2DZ calculations show that the six Cu-N bond distances in [CuL(3)](+) are 2.33, 2.25, 2.32, 2.25, 2.28 and 2.25 angstrom while the ideal Cu(I)-N bond length in a symmetric Cu(I)N(6) moiety is estimated as 2.25 angstrom. Reaction of L with Cu(CH(3)CN)(4)ClO(4) in dehydrated methanol at room temperature even in 4:1 M proportion yields [CuL(2)]ClO(4) (2). Its (1)H NMR spectrum indicates that the metal in [CuL(2)](+) is tetrahedral. The Cu(II/I) potential in 2 is found to be 0.68 V versus NHE in CH(2)Cl(2) at a glassy carbon electrode. In presence of excess L, 2 yields the cyclic voltammogram of 1. From (1)H NMR titration, the free energy of binding of L to [CuL(2)](+) to produce [CuL(3)](+) in CD(2)Cl(2) at 298 K is estimated as -11.7 (+/-0.2) kJ mol (1).

First crystal structures of lanthanide-hydrocinnamate complexes: Hydrothermal synthesis and photophysical studies

Five new lanthanide(III) complexes of hydrocinnamic acid (Hcin), [Ln(cin)3(H2O)3]·3Hcin (Ln = Tb(III) (1), Dy(III) (2), Er(III) (3), Eu(III) (4) and Gd(III) (5)) have been synthesized and characterized. The X-ray structures of 1-5 reveal that all compounds are isostructural and that each lanthanide ion is nine-coordinated by oxygen atoms in an overall distorted tricapped trigonal-prismatic geometry. Six oxygen atoms are provided by carboxylate moieties, and the other three by water molecules. The supramolecular architectures of 1-5 show the presence of uncoordinated hydrocinnamic acid molecules which induce the formation of numerous hydrogen bonds. The photophysical properties of these complexes in the solid state at room temperature were studied using diffuse reflectance (DR), fluorescence excitation and emission spectra. An energy level diagram was used to establish the most relevant channels involved in the ligand-to-metal energy transfer, indicating that cin- ligands can act as intramolecular energy donors for Tb(III), Dy(III) and Eu(III) ions. © 2012 Elsevier B.V.

Aducts of Lanthanide Perchlorates with N,N,N',N'-Tetramethyl Oxydiacetamide

Lanthanide coordination complexes with unidentate and bidentate amide ligands have been widely reported in the literature[l].In contrast, however, coordination compounds with tridentate ligands and with ligands containing ether oxygen as donor atoms to lanthanides have received little attention. In this paper we report the preparation and characterization of complexes formed by the interaction of the lanthanide perchlorates with N, N, N', N'- tetramethyloxydiacetamide (TMODA). The new complexes have been characterized by analysis, conductance, IR and electronic spectra. In addition, ~H and '3C NMR spectra of the ligand and its diamagnetic La ~+ and y3+ complexes are also discussed.