Preparation,NMR studies and crystal structure of mononuclear and dinuclear Pd(II) and Pt(II) complexes that contain 1,2-bis[3-(3,5-dimethyl-1-pyrazolyl)-2-thiapropyl]benzene

The reaction between 1,2-bis[3-(3,5-dimethyl-1-pyrazolyl)-2-thiapropyl]benzene (bddf) and [MCl₂(CH₃CN)₂] (M = Pd(II), Pt(II)) in a 1:1 M/L ratio in CH₂Cl₂ or acetonitrile solution, respectively, gave the complexes trans-[MCl₂(bddf)] (M = Pd(II) (1), Pt(II) (4)), and in a 2:1 M/L ratio led to [M₂Cl₄(bddf)] (M = Pd(II) (2), Pt(II) (5)). Treatment of 1 and 4 with AgBF₄ and NaBPh₄, respectively, gave the compounds [Pd(bddf)](BF₄)₂ (3) and [Pt(bddf)](BPh₄)₂ (6). When complexes 3 and 6 were heated under reflux in a solution of Et₄NBr in CH₂Cl₂/CH₃OH (1:1) for 24 h, analogous complexes to 1 and 4 with bromides instead of chlorides bonded to the metallic centre were obtained. These complexes were characterised by elemental analyses, conductivity measurements, infrared, ¹H, ¹H{¹⁹⁵Pt}, ¹³C{¹H}, ¹⁹⁵Pt{¹H} NMR, HSQC and NOESY spectroscopies. The X-ray crystal structure of the complex [Pd(bddf)](BF₄)₂ · H₂O has been determined. The metal atom is tetracoordinated by the two azine nitrogen atoms of the pyrazole rings and two thioether groups.     

Palladium(II)-allyl complexes containing chiral N-donor ferrocenyl ligands

A study of the reactivity of enantiopure ferrocenylimine (S_C)-[FcCHN-CH(Me)(Ph)] {Fc =  (η⁵-C₅H₅)Fe{(η⁵-C₅H₄)-} (1a) with palladium(II)-allyl complexes [Pd(η³-1R¹,3R²-C₃H₃)(μ-Cl)]₂ {R¹ = H and R² = H (2), Ph (3) or R¹ = R² = Ph (4)} is reported. Treatment of 1a with 2 or 3 {in a molar ratio Pd(II):1a = 1} in CH₂Cl₂ at 298 K produced [Pd(η³-3R²-C₃H₄){FcCHN-CH(Me)(Ph)}Cl] {R² = H (5a) or Ph (6a)}. When the reaction was carried out under identical experimental conditions using complex 4 as starting material no evidence for the formation of [Pd(η³-1,3-Ph₂-C₃H₃){FcCHN-CH(Me)(Ph)}Cl] (7a) was found. Additional studies on the reactivity of (S_C)-[FcCHN-CH(R³)(CH₂OH)] {R³ = Me (1b) or CHMe₂ (1c)} with complex 4 showed the importance of the bulk of the substituents on the palladium(II) allyl-complex (2-4) or on the ferrocenylimines (1) in this type of reaction. The crystal structure of 5a showed that: (a) the ferrocenylimine adopts an anti-(E) conformation and behaves as an N-donor ligand, (b) the chloride is in acis-arrangement to the nitrogen and (c) the allyl group binds to the palladium(II) in a η³-fashion. Solution NMR studies of 5a and 6a and [Pd(η³-1,3-Ph₂-C₃H₃){FcCHN-CH(Me)(CH₂OH)}Cl] (7b) revealed the coexistence of several isomers in solution. The stoichiometric reaction between 6a and sodium diethyl 2-methylmalonate reveals that the formation of the achiral linear trans-(E) isomer of Ph-CHCH-CH₂Nu (8) was preferred over the branched derivative (9). A comparative study of the potential utility of ligand 1a, complex 5a and the amine (S_C)-H₂N-CH(Me)(Ph) (11) as catalysts in the allylic alkylation of (E)-3-phenyl-2-propenyl (cinnamyl) acetate with the nucleophile diethyl 2-methylmalonate (Nu⁻) is reported.     

Crystalline structure and optical spectroscopy of Er3+-doped KGd(WO4)2 single crystals

4 )₂ single crystals doped with Er³⁺ have been grown by the flux top-seeded-solution growth method. The crystallographic structure of the lattice has been refined, being the lattice constants a=10.652(4), b=10.374(6), c=7.582(2) Å, β=130.80(2)°. The refractive index dispersion of the host has been measured in the 350–1500 nm range. The optical absorption and photoluminescence properties of Er³⁺ have been characterised in the 5–300 K temperature range. At 5 K, the absorption and emission bands show the (2J+1)/2 multiplet splittings expected for the C₂ symmetry site of Er in the Gd site. The energy positions and halfwidths of the 72 sublevels observed have been tabulated as well as the cross sections of the different multiplets. Six emission band sets have been observed under excitation of the ⁴F_7/2 multiplet. The Judd–Ofelt (JO) parameters of Er³⁺ in KGW have been calculated: Ω₂=8.90×10^-20 cm², Ω₄=0.96×10^-20 cm², Ω₆=0.82×10^-20 cm². Lifetimes of the ⁴S_3/2, ⁴F_9/2, and ⁴I_11/2 multiplets have been measured in the 5–300 K range of temperature and compared with those calculated from the JO theory. A reduction of the ⁴S_3/2 and ⁴I_11/2 measured lifetimes with increasing erbium concentration has been observed, moreover the presence of multiphonon non-radiative processes is inferred from the temperature dependence of the lifetimes. Received: 15 December 1997/Revised version: 10 July 1998     

Synthesis, crystal structure, and magnetic studies of one-dimensional cyano-bridged Ln3+-Cr3+ complexes with bpy as a blocking ligand

The reaction of Ln(NO3)3.aq with K3[Cr(CN)6] and 2,2'-bipyridine (bpy) in a water/ethanol solution led to two families of complexes: 4 one-dimensional (1D) complexes of the formula trans-[Cr(CN)4(mu-CN)2Ln(H2O)3(bpy)2]n.4nH2O.3.5nbpy (Ln3+ = La, Ce, Pr, and Nd) and 10 1D complexes of the formula trans-[Cr(CN)4(mu-CN)2Ln(H2O)4(bpy)]n.3.5nH2O.1.5nbpy (Ln3+ = Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, and Lu). The structures for the fourteen complexes [LaCr]n (1), [CeCr]n (2), [PrCr]n (3), [NdCr]n (4), [NdCr]n (4'), [SmCr]n (5), [EuCr]n (6), [TbCr]n (7), [DyCr]n (8), [HoCr]n (9), [ErCr]n (10), [TmCr]n (11), [YbCr]n (12), and [LuCr]n (13) have been solved. Complexes 1-4 crystallize in the orthorhombic space group Pbam and are isomorphous; complexes 4'-13 crystallize in the triclinic space group PI and are isomorphous. The X-ray structural characterization of complexes 1-4 shows the presence of a discrete decameric water cluster built around a cyclic hexameric core stabilized by the solid-state structure, which represents another new mode of association of water molecules. The Ln3+-Cr3+ magnetic interaction is negligible in 6 and 12, antiferromagnetic in 2, 4', 7, 8, 9, 10, and 11, and unresolved for 3. The complex 5 is a ferrimagnet because its magnetic studies suggest the onset of a very weak ferromagnetic three-dimensional ordering.     

Formation of Pegylated polyurethane and Lysine-coated polyurea nanoparticles obtained from O/W nano-emulsions

The present work describes the formation of Pegylated polyurethane and Lysine-coated polyurea nanoparticles obtained from O/W nano-emulsions via an interfacial polycondensation process in the aqueous solution/polysorbate 80/diisocyanate/medium chain triglyceride systems. The initial nano-emulsions were prepared using the phase inversion composition (PIC) method. Dynamic light scattering studies revealed the changes in the particle size occurring during the process of nanoparticle formation. Well-defined polymeric nanoparticles with a small particle diameter (below 80 nm) and low polydispersity index were obtained using a highly hydrophilic component (polyethylene glycol or lysine) and an aliphatic diisocyante monomer. FT-IR and AFM studies showed that the polymeric matrix of nanoparticles was built by copolymers derived from reaction between the diisocyanate and the hydroxyl groups of both nonionic surfactant and the highly hydrophilic component. Pegylated-polyurethane and lysine-coated polyurea nanoparticles designed in this study are promising tools for future applications in biomedical sciences.     

Rossinone-related meroterpenes from the Antarctic ascidian Aplidium fuegiense

The chemical analysis of the ascidian Aplidium fuegiense resulted in the isolation of three novel meroterpenoids 2–4, structurally related to the main co-occurring known rossinone B (1). The structures of the new compounds were determined by interpretation of spectroscopic data. Compounds 1–4 were found to be selectively localized in the viscera of the ascidian.     

Determination of grepafloxacin in plasma samples by HPLC: Application to clinical pharmacokinetic studies

Summary A sensitive HPLC assay for the determination of grepafloxacin (GRE) in biological samples is described. Sample preparations were carried out by adding phosphate buffer (pH 7.4, 0.1M), followed by extraction with trichloromethane. GRE and the internal standard, enrofloxacin (ENR), were separated on a reversed-phase column using an aqueous phosphate solution-acetonitrile (78∶22) mobile phase. The concentrations of ENR and GRE eluting of the column with retention times of 2.55, and 4.90 min, respectively were monitored by fluorescence atλ _ex 338 andλ _em 425 nm. The method was shown to be linear from 5 to 4000 ng mL⁻¹. The detection and quantitation limits were 5 and 10 ng mL⁻¹, respectively. Mean recovery was determined as 90%. Inter- and intra-assay precisions were 3.0% and 3.5% respectively. The method was applied to the determination of GRE in plasma samples collected during clinical pharmacokinetic studies.     

Simultaneous determination of difloxacin and its primary metabolite sarafloxacin in rabbit plasma

Summary An HPLC method with fluorescence detection is presented for the analysis of difloxacin (DIF) and sarafloxacin (SAR) in rabbit plasma using norfloxacin (NOR) as internal standard (Figure 1). Plasma sample preparations were carried out by adding phosphate buffer (pH 7.4, 0.1 M), followed by extraction with trichloromethane. Fluoroquinolones were separated on a reversed-phase column using an aqueous phosphate solution-acetonitrile (82:18) mobile phase. The concentrations of NOR, SAR and DIF eluting off the column, with retention times of 2.16, 5.60 and 6.20, respectively, were monitored by fluorescence detection atλ _ex 338 andλ _em 425 nm. The quantitation limit was 12 ng mL⁻¹ for SAR and DIF. Standard curves were linearly related to concentration in the range from 1 to 1500 ng mL⁻¹. Recovery was determined as 76% and 70% for SAR and DIF, respectively. Inter-and intraassay coefficients of variation were less than 6% for all compounds.