Exploitation of dinuclear salan aluminum complexes for versatile copolymerization of ε-caprolactone and L-lactide

By combining the influence of excess alcohol, temperature and monomer-to-initiator ratios in the feed, dinuclear salan aluminum complexes L(R)Al(2)Me(4) exhibited a high degree of control towards the copolymerization of L-LA and ε-CL, producing blocky, gradient, tapered and random copolymers.     

Copolymer of lactide and ε-caprolactone catalyzed by bimetallic Schiff base aluminum complexes

A series of copolymers of lactide(LA) and e-caprolactone(ε-CL) with different monomer feed ratios were achieved using three kinds of bimetallic Schiff aluminum complexes as catalysts. The ratios of LA and ε-CL units in different copolymers and the average segments length were determined by NMR analysis. The comparative kinetic study of L-LA/ε-CL and rac-LA/ε-CL copolymerization systems showed that the polymerization rate of LA was faster than ε-CL, and L-LA showed polymerization rate slightly faster than rac-LA. It was inferred that the copolymers achieved by these complexes were gradient copolymers with gradual change in distribution of LA and e-CL units. The thermal properties of these copolymers were characterized by DSC analysis, which showed that the glass transition temperature(Tg) of these copolymers changed regularly according to the pro-portion change of two structural units.     

Bimetallic aluminum alkyl complexes as highly active initiators for the polymerization of ε-caprolactone

Two dinuclear aluminum alkyl complexes supported by a piperazidine-bridged bis(phenolato) group were prepared, and both complexes exhibited extremely high activity for the ring-opening polymerization of ε-caprolactone. In the presence of benzyl alcohol (BnOH), the polymerization accelerated dramatically.     

Synthesis of 5,1′-alkynyl- and 5,1′-alkenyl-1,3-cyclohexadiene-tricarbonyliron complexes using aluminum reagents

Dimethylaluminum acetylides react with (η⁵-cyclohexadienyl)tricarbonyliron fluoroborate (1) to give the corresponding C(5) alkynyl substituted complexes in high yields without competing reduction products. Using this method, phenylethynyl and trimethylsilylethynyl groups have been added to the cationic complex at C(5). In the latter case, the yield can be improved substantially if tris(trimethylsilylethynyl)-aluminum is used instead. Desilylation of this complex yields the 5-ethynyl complex. Hydrogenation with Lindlar's catalyst yields the corresponding alkenyl complex. Oxidative removal of the Fe(CO)₃ moiety yields the organic ligand in near quantiative yields. Use of aluminum reagents as alkynyl anion synthons in reactions with 1 is a far superior method compared to the use of either lithium acetylides which give complicated mixtures of products or 1-trimethylsilylalkynes which are unreactive.     

Investigation of the presence of KCl in the structure and morphology of V-amylose–inclusion complexes

Amylose–fatty acid inclusion complexes were prepared using amylose extracted from pea starch and fatty acids with different chain length. To form the complexes, amylose, dissolved in aqueous alkaline solution (0.1 Ν ΚΟΗ), was mixed with fatty acid potassium soap solution and after neutralization the complex was obtained as precipitate. To investigate the structure and morphology of V-amylose–inclusion complexes, a series of techniques such as X-ray diffraction, SEM-microscopy combined with elemental microanalysis, Differential scanning calorimetry and Fourier transform infrared spectroscopy were employed. XRD analysis of complexes, revealed that the complexes displayed the typical V-form pattern, with an extra peak at 2θ?=?28.2°. To identify the origin of that peak the complexes were examined by SEM microscopy combined with elemental microanalysis. The results indicated that the peak was due to the presence of potassium chloride, formed during the preparation of the complexes. Washing the complexes with water was sufficient to remove the salt.     

Complexation of hypocrellins and bivalent metals and one-electron reduction of the complexes with electron donor

The complexation of HA (or HB) with bivalent metals was examined by UV-Vis andNMR spectroscopy, and all of the complexes obtained have a metal-ligand ratio of 1:1.Thephotoinduced reduction of the complexes of HA-Zn~(2+) and HA Mg2+ (or HB-Zn~(2+), HB-Mg2+)in the presence of 1-benzyl-1,4-dihydro-nicotinamide as the electron donor was investigated byUV-Vis and ESR spectroscopy. The studies demonstrated that illumination of the complexes ofHA(HB)-Zn~(2+) and HA(HB)-Mg~(2+) led to the accumulation of the chelated semiquinone radicalanions.     

β-Diketiminate complexes of Group 4: active complexes for the isomerization of α-olefins and the polymerization of propylene towards elastomeric polypropylene

The β-diketiminate lithium ligand [{N(SiMe₃)C(Ph)}₂CH][Li] reacted with Group 4 metal salts (Ti and Zr) to yield the complexes [{N(SiMe₃)C(Ph)}₂CH]₂TiCl₂ (5) and [{N(SiMe₃)C(Ph)}₂CH][N(SiMe₃)C(Ph)NC(Ph)CH(SiMe₃)]ZrCl₂ (6). The crystal structure of 6 shows that one of the two ketamidinate ligands undergoes an isomerization to the corresponding substituted benzamidinate. A mechanism for the catalyzed isomerization of the β-diketiminate ligand is presented. Complex 5 was found to be active in the polymerization of propylene, producing remarkably high-molecular weight (>100,000 g mol⁻¹) elastomeric polymer, whereas the zirconium complex was found inactive. Complex 5, and surprisingly complex 6, were found to be active catalysts, in the presence of MAO (methylalumoxane), for the isomerization of aliphatic olefins (1-octene, allylbenzene). Each complex catalyzed the olefins by different mechanisms. Kinetic studies for the isomerization of allylbenzene by complex 5 show that the reaction rate follows a first order in both catalyst and olefin concentrations with ΔH^‡=14.7(4) kcal mol⁻¹ and ΔS^‡=−33(1) e.u. These findings support the epimerization mechanism of the last inserted monomer that is proposed for as the primary cause for the elastomeric properties of polypropylene produced by this complex. In addition, we show how complementary isomerization studies of α-olefins shed light on the polymerization mechanism.     

Synthesis and structures of 3-sila-β-diketiminato complexes of the coinage metals

The dimeric copper(I) 3-sila-β-diketiminate [Cu{(N(R)C(Ar))₂SiR}]₂ · (thf) (1) was obtained from CuI and [Li{(N(R)C(Ar))₂SiR}(thf)₂] (B) in toluene (R = SiMe₃, Ar = C₆H₃Me₂-2,6). When [CuI(PPh₃)₃] was used as a starting material, the LiI-containing compound [Cu{Si(R)(C(Ar)N(R))₂Li(μ-I)}(PPh₃)] (2) was isolated. The reaction of [MI(PPh₃)_n] (M = Ag, n = 3; M = Au, n = 2) with two equivalents of B in toluene gave the isomorphous silver and gold 3-sila-β-diketiminates [M{Si(R)(C(Ar)N(R))₂Li}₂(μ-I)] [M = Ag (3), Au (4)]. Each of 1-4 was characterised by the multinuclear NMR spectroscopy and single-crystal X-ray diffraction crystallography.     

Synthesis and structure of metalloid aluminum clusters—intermediates on the way to the elements

Metastable Aluminum(I) halide solutions proved to have a high potential for the synthesis of novel subvalent Al compounds, such as Al_nX_m species (X=Cl, Br, I; n<m, average oxidation state of Al below +3 or n>m, average oxidation state of Al below +1) or Al_nR_m species (R=bulky ligand; n>m). There are two principal reaction types, which are essential for the formation of the compounds discussed herein. The disproportionation, which finally results in Al(III) halides and Al metal and the metathesis which leads to a substitution of X atoms against R groups. By this way the metalloid cluster compounds [Al₇{N(SiMe₃)₂}₆]⁻, [Al₁₂{N(SiMe₃)₂}₈]⁻, [Al₁₄I₆{N(SiMe₃)₂}₆]²⁻, [Al₆₉{N(SiMe₃)₂}₁₈]³⁻, and [Al₇₇{N(SiMe₃)₂}₂₀]²⁻ could be isolated. The characteristic feature of these metalloid Al clusters is the number of AlAl contacts being larger than the number of Alligand bonds, i.e. there are more ‘naked’ than ligand-bonded Al atoms. Furthermore, the topology of the closest packing in Al metal is already pre-formed in these compounds.     

Electrochemical and associated techniques for the study of the inclusion complexes of thymol and β-cyclodextrin and its interaction with DNA

Journal of Solid State Electrochemistry - Thymol, a potent agent for microbial, fungal, and bacterial disease, has low aqueous solubility and it is genotoxic, i.e., is capable of damaging...     

An oxidation system for green chemistry – synthesis of bi-metallic schiff base complexes and oxidation of phenols in the presence of the complexes –

Bimetallic copper complexes were synthesized from the schiff bases which were obtained by the reaction between bis(3-aminophenyl) sulphone and salicylaldehyde and the derivatives in order to clarify the active site of the immobilized polymer catalyst. The complex-H₂O₂ system showed effective oxiation of phenols. The active site was elucidated by UV spectrum.     

Determination of the stoichiometry and stability constants of theβ-cyclodextrin-dextromethorphan inclusion complexes by liquid chromatography and UV spectroscopy

The inclosion of dextromethorphan (DMN) by -cyclodextrin (-CD) was studied by using chromatography, UV spectroscopy and circular dichroism methods at 25 °C, pH 7.4 and 4.2. It was found that the CD : DMN complex has 1 : 1 stoichiometry. It is more stable at pH 7.4 than at pH 4.2. with constants respectively equal to 8000 ± 800 M^–1 and 5750 ± 500 M^–i, as determined by chromatography. The stability of the complex at pH 7.4 decreases as the temperature increases. From the van 't Hoff dependence the standard entropy and enthalpy changes were determined at this pH.     

Excimer fluorescence and structures of the inclusion complexes of β-cyclodextrin with naphthalene and its derivatives

Fluorescence of the inclusion complexes with different compositions formed by naphthalene-h₈, naphthalene-d₈, 2,7-dimethylnaphthalene (DMN), and 2-benzylnaphthalene (BN) with β-cyclodextrin (β-CD) in water was studied. Two types of fluorescence are observed, monomer (MF) and excimer (EF_ fluorescence. The excimer fluorescence of the 2∶2 complex emitted by aggregated light-dispersing crystals forming a precipitate, whereas is the MF is concentrations, EF predominates for the resulting complexes. A proposed structure of the inclusion complexes was derived from MNDO/PM3 semiempirical quantum-chemical calculations. The EF is caused by the structure of the complex, in which both naphthalene molecules are separated by a distance of 4.7 Å: they lie in parallel orientation to each other, whereby one ring is displaced from the other by one-fourth of the length of the naphthalene ring. The complexes of 2,7-DMN and 2-benzylnaphthalene with β-CD do not exhibit EF. For the 2∶2 complex of 2,7-DMN with β-CD, this is due to the fact that the aromatic fragments are removed too far from one another 2-Benzylnaphthalene is unable to form an inclusion complex with β-CD, in whose structure the aromatic fragments inside the cavity could be arranged in parallel planes; instead, it forms a 1∶2 complex with β-CD.     

Spectroscopic and electrochemical study of dinuclear and mononuclear copper complexes with the bidentate ligand of the 2,2′-diquinoline series

The newly synthesized complex (2) of copper(I) chloride with di-n-hexyl 2,2′-biquinoline-4,4′-dicarboxylate (L) was spectroscopically and electrochemically characterized. The X-ray diffraction study showed that the crystals of complex 2 consist of the dinuclear moieties [L₂Cu¹ ₂(μ-Cl)₂] containing Cu₂(μ-Cl)₂ clusters. Spectrophotometric studies and ESI-mass spec-trometric measurements showed that after the dissolution of complex 2 in acetonitrile (AN) and N-methyl-2-pyrrolidone (NMP), the solution contained not only the dinuclear complexes [L₂Cu¹ ₂(μ-Cl)₂] but also [L₂Cu¹]Cl, [LCu¹Cl(Sol)], and [Cu¹Cl(Sol)] (Sol is the solvent). The electrochemical data also confirm the conclusion that bridged dinuclear chloride complex 2 dissociates both in NMP and AN to form the tetrahedral bis-biquinoline complex [L₂Cu¹]Cl. In solutions of complex 2 in alcohols and _N,_N-dimethylformamide (DMF), only [L₂Cu¹]Cl and [Cu¹Cl(Sol)] are present. In EtOH, AN, and DMF, [Cu¹Cl(Sol)] undergoes disproportionation to [Cu¹¹Cl(Sol)] and Cu⁰.     

A spectrophotometric determination of the formation constants of the inclusion complexes ofα- andβ-cyclodextrins with the azonium and ammonium tautomers of methyl orange and methyl yellow

The color fading caused by the addition of-cyclodextrin or-cyclodextrin to an aqueous solution of a tautomeric mixture of methyl orange or methyl yellow is studied spectrophotometrically at pH 1.1 and 25.0°C. A model involving 1 : 1 stoichiometry has been used to analyze the spectrophotometric data. The addition of a cyclodextrin shifts the tautomeric mixture towards the side of the ammonium tautomer. An expression allowing the calculation of the tautomeric equilibrium constant of the inclusion complexes is derived. The formation constants of the inclusion complexes of the individual tautomers are determined. Both- and-cyclodextrins bind the ammonium tautomer stronger than the azonium tautomer. The inclusion complexes of-cyclodextrin are more stable than the corresponding ones of-cyclodextrin.     

The determination of the stability constants of the lanthanide α-hydroxyisobutyrate and lactate complexes by potentiometric titration

The stability constants of the lanthanide and yttrium, complexes with α-hydroxyisobutyrate and lactate, have been determined by potentiometric titration. The average numbor of ligands bound per metal ion has been calculated by the method of calvin-wilson and indicates the formation of uninegative tetra-ligand complexes of the form ML₄-. The ₄ formation constants have been derived by ₄ procedures; bjerrum's half-n¯;-method. fronaeus' and poulsen's extrapolation methods, and by least squares calculation, using an IBM 1620 digital computer.     

Theoretical and experimental investigations of the enantioselective epoxidation of olefins catalyzed by manganese complexes

The enantioselective epoxidation of olefin by Mn^II（R,R-PMCP）(OTf)2, H₂O₂ and H₂SO₄ was explored by DFT calculations and experiments. Theoretical results suggest that [MnV（O）(R,R-PMCP)（SO4）]+species with a triplet ground spin state serves as the active species for the olefin epoxidation. It can be generated by the H₂SO₄ assisted O-O heterolysis of Mn^III（OOH） species. Mn^III-persulfate is also involve...