Pentacoordinate nickel(II) complexes double bridged by phosphate ester or phosphinate ligands: spectroscopic, structural, kinetic, and magnetic studies

The bis(phosphatediester)-bridged complexes [[Ni([12]aneN(3))(mu-O(2)P(OR)(2))](2)](PF(6))(2) [[12]aneN(3)=Me(3)[12]aneN(3), 2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene; R=Me (1), Bu (2), Ph (3), Ph-4-NO(2) (4); [12]aneN(3)=Me(4)[12]aneN(3), 2,4,4,9-tetramethyl-1,5,9-triazacyclododec-1-ene; R=Me (5), Bu (6), Ph (7), Ph-4-NO(2) (8)] were prepared by hydrolysis of the phosphate triester with the hydroxo complex [[Ni([12]aneN(3))(mu-OH)](2)](PF(6))(2) or by acid-base reaction of the dialkyl or diaryl phosphoric acid and the above hydroxo complex. The acid-base reaction was also used to synthesise the phosphinate-bridged complexes [[Ni([12]aneN(3))(mu-O(2)PR(2))](2)](PF(6))(2) [[12]aneN(3)=Me(3)[12]aneN(3), R=Me (9), Ph (10); [12]aneN(3)=Me(4)[12]aneN(3), R=Me (11), Ph (12)]. The molecular structures of complexes 2, 3 and 12 were established by single crystal X-ray diffraction studies. The eight-membered rings defined by the nickel atoms and the bridging ligands show distorted twist-boat, chair and boat-boat conformations in 2, 3 and 12, respectively. The experimental susceptibility data for compounds 2, 3 and 12 were fitted by least-squares methods to the analytical expression given by Ginsberg. The best fit was obtained with values of J=-0.11 cm(-1), D=-9.5 cm(-1) and g=2.20 for 2; J=-0.97 cm(-1), D=-9.3 cm(-1) and g=2.21 for 3; and J=-0.14 cm(-1), D=-11.9 cm(-1) and g=2.195 for 12. The magnetic-exchange pathways must involve the phosphate/phosphinate bridges, because these favour antiferromagnetic interactions. The observation of a higher exchange parameter for compound 3 is a consequence of a favourable disposition of the O-P-O bridges. The kinetics for the hydrolysis of TNP (tris(4-nitrophenyl)phosphate) with the dinuclear nickel(II) hydroxo complex [[Ni(Me(3)[12]aneN(3))(mu-OH)](2)](PF(6))(2) was studied by UV-visible spectroscopy. The proposed mechanism for TNP-promoted hydrolysis can be described as one-substrate/two-product, and can be fitted to a Michaelis-Menten equation.     

Transition-Metal Complexes with Nano-Sized Phosphine and Pyridine Ligands-Catalysis,Fluxional Behavior and Molecular Recognition

Nano-sized phosphine and pyridine ligands having tetraphenylphenyl-, m-terphenyl-, poly(benzylether) moieties were synthesized. These ligands showed a remarkable effect on homogeneous transition metal catalyzed reactions. Pd(II) complexes with tetraphenylphenyl substituted pyridine ligands show high catalytic activities for oxidation of ketones suppressing Pd black formation and maintains the catalytic activity for a long time. Rh(I) complex catalysts with m-terphenyl substituted phosphine ligands showed remarkable rate acceleration in the hydrosilylation of ketones. In addition, several phosphinocalixarene ligands were synthesized and their coordination studies with Pd(II), Pt(II), Ru(II), Ir(I), and Rh(I) metals were documented. Ir(I) and Rh(I) cationic complexes with a 1,3,5-triphosphinocalix[6]arene ligand showed dynamic behavior with size-selective molecular recognition.     

Oxidation of α-methylstyrene on an MCM-22 encapsulated (<Emphasis Type="Italic">R,R</Emphasis>)-(−)-<Emphasis Type="Italic">N,N′</Emphasis>-bis(3,5-di-<Emphasis Type="Italic">tert</Emphasis>-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II) catalyst

(R, R)-(−)-N, N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II) was encapsulated into MCM-22 using the zeolite synthesis method. The encapsulated catalyst proved to be active in the oxidation of α-methylstyrene with NaOCl with higher specific activity than the homogeneous catalyst. At the same time, this encapsulated catalyst was completely inactive in the hydrolytic kinetic resolution of racemic styrene oxide. This observation is in a good correlation with the assumption of the cooperative bimetallic mechanism proposed by Annis and Jacobsen.     

Thermogravimetry as a screening tool for the estimation of the vapor pressures of pure compounds

A simplified approach was developed to estimate the vapor pressure of pure compounds from experimental data obtained by isothermal thermogravimetric (TG) analysis. A numerical procedure was developed to estimate the Antoine parameters of the substance by the analysis of isothermal TG data. The results of the experimental validations carried out evidenced that at least a preliminary estimation of vapour pressures of pure substances by the analysis of TG data is possible. The limited time and the reduced amounts of sample required for the experimental runs make the technique attractive with respect to the conventional and more accurate techniques for vapor pressure assessment.     

Hydroformylation of Olefins Catalyzed by Rhodium Trichloride Anchored on Ti-HMS

Rhodium trichloride supported on Ti-hexagonal mesoporous silica (Ti-HMS), via a bipyridyl group, is an efficient catalyst for the hydroformylation of olefins at 120 °C and 40.8 atm of CO/H₂ (CO/H₂=2/1). The catalyst is selective leading to high ratios of linear or branched aldehydes from functionalized olefins, and high activity in the case of propene which gave a turnover frequency of 6209 mol/mol(Rh)/h.     

The role of salt on cellulose dissolution in ethylene diamine/salt solvent systems

Ethylene diamine (EDA)/salt solvent systems can dissolve cellulose without any pretreatment. A comparison of the electrical conductivity of different salts in EDA was made at 25 °C, and conductivity decreased in the order of KSCN>KI>NaSCN at the same molar concentration. Among the salts tested, potassium thiocyanate (KSCN) was capable of dissolving both high molecular weight (DP>1000) and low molecular weight (DP = 210) cellulose, and this was confirmed by polarized light microscopy. ³⁹K and ¹⁴N NMR experiments were conducted at 70 °C as a function of cellobiose concentration with EDA/KSCN as the solvent. The results showed that the K⁺ ion interacts with cellobiose more than the SCN⁻ ion does. Recovered cellulose was studied by infrared spectroscopy (FTIR) and wide angle X-ray diffraction (WAXD). Changes in the FTIR absorption bands at 1,430 and 1,317 cm⁻¹ were associated with a change in the conformation of the C-6CH₂OH group. The changes in positions and/or intensities of absorption bands at 2,900, 1,163, and 8,97cm⁻¹ were related to the breaking of hydrogen bonds in cellulose. X-ray diffraction studies revealed that cellulose, recovered by precipitating cellulose solutions with water, underwent a polymorphic transformation from cellulose I to cellulose II.     

Preparation of high molecular weight polyurethane particles by nonaqueous emulsion polyaddition

A versatile nonaqueous emulsion polyaddition process for the one-step fabrication of spherical polyurethane nanoparticles is presented. Three different emulsion systems were used consisting of N,N′-dimethylformamide (DMF) dispersed in n-hexane, acetonitrile dispersed in cyclohexane, and acetonitrile dispersed in tetradecane. After successful stabilization of the emulsion systems by using a poly(isoprene)-poly(methylmethacrylate) block copolymer, the fabrication of the polyurethanes was carried out within the dispersed polar phase. The polyurethane particles showed average diameters as small as 35 nm. Additionally, infrared (IR) characterization revealed that the formation of any urea, which decreases the mechanical properties of the polyurethanes, was prevented during the polyaddition. This was attributed to the anhydrous reaction conditions. Gel permeation chromatography (GPC) analysis demonstrated the average molecular weights (M _n) of the polyurethanes to be as high as 16,500 g/mol, corresponding to conversions of 0.98. Comparable molecular weights and conversions have not previously been achieved without the formation of urea.     

The synthesis and characterization of a new (<Emphasis Type="Italic">E,E</Emphasis>)-dioxime containing 13-membered dithiadiazamacrocyclic moieties and its mononuclear complexes

A new (E,E)-dioxime, (6Z,7Z)-15,16-dihydro-14H-dibenzo[b,h][1,10,4, 7]dithiadiazacyclotride-cine-6,7(5H,8H)-dionedioxime (H ₂ L) has been synthesized by reacting cyanogen-di-N-oxide (2) with 2,2′-[propane-1,3-diylbis(thio)]dianiline (1). Mononuclear complexes (4) and (5) of this ligand have been synthesized by reacting the vic-dioxime (H₂L) with NiCl₂ · 6H₂O and CoCl₂ · 6H₂O, respectively. The BF ₂ ⁺ capped Ni(II) and Co(III) complexes (6) and (7) of the dioxime have been synthesized from (4) and (5). The new compounds were characterized by a combination of elemental analysis, ¹H- and ¹³C-n.m.r, i.r. and m.s. spectral data.     

Polymer dispersions from catalytic polymerization in aqueous systems

By contrast to traditional free radical emulsion polymerization, catalytic polymerization allows for polymer microstructure control. In terms of polymerizable monomers, both techniques are largely complementary. Since the beginning of this decade, an increasing number of reports on polyolefin, polybutadiene, polyalkenamer, polynorbornene, polyketone, and polyacetylene dispersions prepared by catalytic polymerization in disperse aqueous systems has appeared. This contribution reviews the preparation of these dispersions, their colloidal properties, particle formation mechanisms, particle morphologies, and polymer microstructures.     

Thermal behavior of polyacrylonitrile polymers synthesized under different conditions and comonomer compositions

Polyacrylonitrile (PAN) polymers are used as precursors for carbon fiber production. This process requires an oxidative stabilization step, which can be studied by differential scanning calorimetry (DSC). In this sense, thermal behavior of PAN based terpolymers by different polymerization processes, compositions and itaconic acid concentrations in the reaction media were investigated. The obtained results showed that the addition of itaconic acid and methyl acrylate as comonomers resulted a lower heat flow during the process comparing to the PAN homopolymer. It suggested that these comonomers aid the oxidative stabilization stage for all studied process. The redox system polymerization at 40°C resulted in a lower heat flow. Itaconic acid decreases slightly initial and peak temperatures of the terpolymer and heat flow until concentration of 3y. The cyclization temperature decreases when MAis incorporated into the terpolymer compared to the MMA terpolymer and increases when MAA is the acidic monomer. Among terpolymers the AN/MA/AA polymer showed the best thermal behavior for carbon fiber producing.