The diastereoselectivity of addition reaction of crotylmetal reagents to cobalt-complexed acetylenic aldehydes and metal-free aldehydes was examined. The anti-diastereomer was the predominant product when the crotyl metallics were Cr, Sn, and Zr. In THF, the uncomplexed aldehydes normally gave higher anti-diastereoselectivity. However, the cobalt-complex of silicon-substituted propynals with three bulky substituents produced increased proportions of syn-diastereomer. In DMF, the selectivity shifted towards syn-isomer except in the case of dimethylphenylsilyl substituent. When tributylstannane was used in the presence of BF3 etherate, moderate syn- selectivity was observed with uncomplexed aldehydes, but only decomposed products from complexed aldehydes.

A new series of polyarylate copolyesters were prepared by melt polycondensation of 1,4-diacetoxy-2,5-(α-phenylisopropyl)benzene with mixture of terephthalic acid and isophthalic acid in varying ratio. And their general properties such as the glass transition temperature, crystalline melting temperature, crystallinity and solubility were studied. The intrinsic viscosity values of the present polymers measured in a mixed solvent of phenol/p-chlorophenol/1,1,2,2-tetrachloroethane ranged from 0.45 to 0.66 depending on the composition and molecular weight. The copolyesters containing greater than 20 mole % of isophthalic acid were found to be amorphous, whereas the homopolymer derived from terephthalic acid was semicrystalline with a melting point of 414℃. The glass transition temperatures of the polymers ranged from 165 to 180℃ depending on the composition. The copolyesters containing 50 mole % and greater of isophthalic acid moiety were soluble at room temperature in such common solvents as tetrahydrofuran, chloroform and N,N-dimethylformamide.

Electrochemical reduction of oxygen has been carried out at glassy carbon electrode and carbon ultramicroelectrode, the surface of which is modified with a new Co(Ⅱ)-Schiff base complex, Co(Ⅱ)-3,4-bis(salicylidene diimine)toluene in 1 M KOH solution. The results obtained from cyclic voltammetric and chronoamperometric experiments are consistent with the formation of the reasonably stable superoxide ions as a primary electron transfer reaction product. The exchange rate constant obtained for oxygen reduction is about 0.02 cm/s.

Six-coordinate molybdenum(Ⅴ)-oxo complexes (PyH)[MoOCl2L] and (R4N)-[MoOCl2L] (R=CH3 and C2H5) with N-salicylidene-2-aminophenol(L1) and its derivatives(L2=5-CH3, L3=3-CH3O, L4=5,6-C4H4 and L5=5-NO2) as ONO-donor ligands have been synthesized and the spectral and electrochemical properties of the complexes by elemental analysis, molar conductivity, UV-vis, IR, 1H NMR and CV have been studied.

UV photolysis of the titled polysilane (Me3Si)3SiMe (I) in the presence of a trapping agent of 2-propenol has been performed to investigate the interaction of short-lived silicon species formed from the photolysis of I with 2-propenol. Product studies show that the Me(Me3Si)Si: (II) and (Me3Si)3Si${\cdot}$(III) are primarily formed as the major reactive species which saturate their valencies via O-H insertion and H-abstraction, respectively. Some products are unstable toward further secondary reaction such as photodissociation and intermolecular reaction. The PM3 semiempirical calculations are performed to deduce the energetics of the photoinduced chemical reactions of I with the substrate.

Macrocyclic ligands have been studied as cation carriers in a supported liquid membrane system. Cd2+ has been transported using nitrogen substituted macrocycles as carriers and several divalent metal ions (M2+=Zn, Co, Ni, Cu, Pb, Mg, Ca, and Sr) have been transported using DBN3O2, DBN2O2and PolyNtnoen as carriers in a supported liquid membrane system. Competitive Cd2+-M2+ transport studies have also been carried out with the same system. Ligand structure, stability constant, membrane solvent and carrier concentration are also important parameters in the transport of metal ions.

Reactions of alkenes and alkynes with the recently discovered isopinocampheylhaloborane-methyl sulfide (IpcBHX·SMe2, X=Cl, Br, I) were investigated in detail in order to establish their usefulness as hydroborating agents. The reagents readily hydroborated alkenes at 50 ℃ and alkynes at 25 ℃ with excellent regioselectivity in placing the boron atom exclusively at the less hindered carbon atom. Especially, the selectivity achieved by the iodo derivative reaches essentially 100%. In addition to that, IpcBHX·SMe2 was applied to the reduction of cyclic ketones to examine its stereoselectivity. The halogen substituent in these reagents plays an important role in the stereoselective reduction. The stereoselectivity increased dramatically with increasing steric size of the substituent. Finally, the iodo derivative achieved highly stereoselective reduction, such selectivity being comparable to that previously achieved with trialkylborohydrides.

Interpolymer complex formation between basic polypeptide poly(L-proline) Form Ⅱ (PLP(Ⅱ)) and acidic polypeptides poly(L-glutamic acid) (PLGA) and poly(L-aspartic acid)(PLAA) has been studied in water-methanol (1:2 v/v) mixed-solvent by viscometry, potentiometry, light scattering and circular dichroism (CD) measurements. It has been found that polymer complexes between PLP(Ⅱ) and PLGA (or PLAA) are formed via hydrogen bonding with a stoichiometric ratio of PLP(Ⅱ)/PLGA (or PLAA)=1:2 (in unit mole ratio) and that PLP(Ⅱ) forms polymer complex more favorably with PLGA than with PLAA. In addition, the minimum (for pH 5.0) and the maximum (for pH 3.2) in reduced viscosity of dilute PLP(Ⅱ)-PLGA mixed solutions are observed at 0.67 unit mole fraction of PLGA (i.e., [PLP(Ⅱ)]/[PLGA]=1/2). These findings could be explained in terms of molecular structure (or conformation) of the complementary polymers associated with the complex formation.

The mechanism of the photodecomposition of 2-methoxy-1,2-diphenyl diazoethane has been investigated in methanol and isoprene using time-resolved laser flash photolysis techniques. The reaction of triplet carbene which is generated from 2-methoxy-1,2-diphenyl diazoethane with methanol is believed to proceed via thermal excitation to the singlet state. The activation energy and enthalpy are consistent with a mechanism involving thermal equilibrium between the triplet and singlet state followed by the reaction of the singlet with methanol to give ether.

Heats of solution of aniline (AN), benzylamine (BA), ethyl-(EBS) and 2-phenylethyl benzenesulfonates (PEB) are calorimetrically measured in acetonitrile-methanol mixtures at 25.0 $^{\circ}C$. The activation parameters, ${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$ and ${\Delta}G^{\neq}$, are determined for the reactions of EBS and PEB with AN and BA using the kinetic data at three temperatures. Calorimetric transfer enthalpies of initial state, ${\delta}H_t^{0{\rightarrow}x})$(IS), and kinetically derived activation enthalpies, ${\delta}\;{\Delta}H^{\neq}$, in the MeCN-MeOH mixtures are combined to determine the transfer enthalpies of transition state, ${\delta}H_t^{0{\rightarrow}x})$(TS); ${\delta}H_t^{0{\rightarrow}x})$(IS) = ${\delta}{\Delta}H^{\neq}\;+\;{\delta}H_t^{0{\rightarrow}x}$(IS) The preferential solvation of anionic charge in the TS predicts a loose TS with a greater degree of bond cleavage for the reactions of PEB than for EBS, and also for the reactions with BA compared to the reactions with AN.

Substituted 3-phenyl-1-silabutanes such as 3-phenyl-1-silabutane (1), 3-(2,5-dimethylphenyl)-1-silabutane (2), 3-(p-chlorotolyl)-1-silabutane (3), and 3-naphthyl-1-silabutane (4) were prepared in 62-96% yield by reduction of the corresponding substituted 3-phenyl-1,1-dichloro-1-silabutanes with LiAlH4. The dehydrogenative polymerization of the monomer silanes was carried out with Cp2MCl2/Red-Al (M=Ti, Hf) catalyst system. The molecular weight of the polymers produced ranged from 700 to 1300 (vs polystyrene) with degree of polymerization (DP) of 5 through 16 and with polydispersity index (PDI)=1.1-2.1. The dehydrogenative polymerization of the monomer silanes with Cp2TiCl2/Red-Al catalyst system occurred at a faster rate and produced somewhat higher molecular weights of polysilane than that with Cp2HfCl2/Red-Al catalyst system.

New compounds of melaminium 2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane-4-methoxy-sulfate have been synthesized and characterized by means of chemical analysis, 1H, 13C, and 31P NMR, and IR spectroscopies. When the compounds are subjected to an open flame, they foam without melting to produce a light char with about 50 times volume of the initial compounds. The evaluation of these flame-retardants proves to be efficient for polypropylene. Thermogravimetric analysis discloses that the compounds are also thermally stable for compounding into polypropylene without decomposition.