Hydrocarbon solution of $Cp_2Zr(CH_3)Cl$ react rapidly with $Na_2Fe(CO)_4$ (1/2 equiv.) to yield $[Cp_2Zr(CH_3)]_2Fe(CO)_4$ and NaCl. The more soluble metal-metal bonded complex $[Cp_2ZrC_8H_{17}]_2Fe(CO)_2$ has also been prepared through the reaction of $Cp_2Zr(C_8H_{17})BF_4$ and $Na_2Fe(CO)_4 (1/2 equiv.). The complexes were characterized by IR, $^1H$ NMR, ^{13}C$ NMR, and elemental analysis. The infrared spectrum of $[Cp_2ZrR]_2Fe(CO)_4$ shows four bands, which is indicative of a cis-structure. The $^{13}C$ NMR spectrum provides evidence for the cis-structure.

The solvent coordination effect on the excited state processes of Mg(II)- and Zn(II)-phthalocyanines has been described. The triplet state of these compounds decays with mixed first and second order kinetics or mainly second order kinetics depending on the solvents used. The first order component of the rate constants decrease along with the series, dimethylsulfoxide (5-coordinated), 1-chloronaphthalene (4-coordinated) and piperidine (6-coordinated), while the second order rate constant is dependent on the diffusion rate constant of the solvents. The excited state quenching by methylviologen or p-benzoquinone is discussed. And ion recombination rate constant is given.

New di- and triorganotin(IV) complexes of meta- and para-phenylenebisdithiocarbamate(m- and p-pbdtc) have been synthesized and characterized by means of chemical analysis, mass spectrometry, and IR spectroscopy. The reaction of the m-pbdtc ligand with diorganotin(IV) halides resulted in 1:1 products, $R_2Sn{\cdot}m$-pbdtc (R = Me, Cy, n-Bu) of dimeric nature whereas the p-pbdtc ligand led to an oligomeric or polymeric structure. The pbdtc ligands were also reacted with triorganotin(IV) halides to form monomeric complexes, $(R_3Sn)_2{\cdot}pbdtc.$ The tin coordination chemistry of these complexes were also discussed in terms of Sn-C and Sn-S bonding modes.

A new heterocuprate containing 2-pyridyloxy ligand, lithium 2-pyridyloxy-n-butylcuprate, has shown improved thermal stability and it reacts with acid chlorides to afford the corresponding ketones in high yields. Similarly, it can be effectively utilized in conjugate addition reactions of $\alpha,\beta$-unsaturated ketones. Of synthetic significance is that the complete utilization of n-butyl group in lithium 2-pyridyloxy-n-butylcuprate has been observed.

It is demonstrated by using a highly positive uranium ion as a test case that the exact relation between the small and the large components of a Dirac spinor in relativistic self-consistent-field (RSCF) calculations is not fully satisfied by the kinetic balance condition only even for two electron systems. For a fixed number of large component basis functions, total energies are sensitive to the change of the size of the small component basis sets even after the kinetic balance condition is fully satisfied. However, the kinetic balance condition appears to be a reasonable guideline in generating reliable and practical basis sets for most applications of RSCF calculations. With a complete small component basis set, energies from RSCF calculations exhibit a variational behavior, implying the stability of the present RSCF procedure.

Two new types of NMR shift reagents, one giving dipolar-only and the other giving contact-only shifts, can be prepared simply by mixing two appropriate $Ln(fod)_3$(Ln = Pr, Nd, Eu, and Yb) reagents in certain ratios. The $^1H$ and $^{13}C$ NMR spectra of pyridine-type substrates, quinoline and isoquinoline, whose paramagnetic shifts are normally a composite of contact and dipolar contributions with single lanthanide shift reagents, show the feasibility of this approach.

A number of Korean potsherd samples has been classified by Fisher's discriminant method for the training set of Kyungki, Koryung and Kyungnam groups. The Koryung samples have been further classified for the training set of Koryung A, B and C subgroups. The training sets have been used to define classification of unknown samples and clay samples so as to find out some similarity between clay samples and certain potsherd groups.

Starting with the readily available p-tert-butyl-calix[4]arene 2, tert-butyl groups are removed by $AlCl_3$-catalyzed de-alkylation reaction, and the calix[4]arene 3 formed is converted to the tetraacetate 4. This compound undergoes Fries rearrangement to yield p-acetylcalix[4]arene 6, which seems to be an attractive starting material for the introduction of functional groups. As a preliminary experiment p-(1-hydroxyethyl)calix[4]arene 7 is prepared by LiAlH$_4$ reduction of 6.

Optically active (R,Z)-(-)-5-tetradecen-4-olide, the pheromone of Popillia japonica Newman was synthesized from (R)-2,3-O-isopropylideneglyceraldehyde as starting material. The biological activity test of the synthetic pheromone as attractant for the male Japanese beetle was tested in Korea.

Two contributions to the activation barrier of the $S_N2$ reaction, intrinsic and thermodynamic, are discussed in connection with the predictive power of various rate-equilibrium relationships. It has been shown that the PES models can only give correct predictions of changes in structure and energy of the transition state if the activation barrier is dictated by the thermodynamic factor. We concluded that the identity and dissociative $S_N2$ reactions are dominated by the intrinsic component while associative $S_N2$ reactions are predominantly of thermodynamic controlled. Thus in the former cases, the PES models fail, whereas in the latter cases predictions based on the intrinsic factor, the quantum mechanical models, fail. Finally in a general case of equal contributions by thermodynamic and intrinsic factors, the $SN_2$ reaction proceeds by a synchronous process with zero net charge on the reaction center, for which predictions of substituent effects will be the same as for the intrinsic control case.

Stereochemical control of the Wittig reaction of the primary aldehyde, 8-acetoxyoctan-1-al (7) with the nonstabilized alkylide, triphenylphosphonium n-butylide (6), was achieved by controlling the reaction conditions including solvent, temperature and inorganic salts. These conditions can be applied to the direct sythesis of the mixture of (Z)-, and (E)-8-dodecen-1-yl acetate, the sex pheromone of the oriental fruit moth, Grapholitha molesta. The primary aldehyde, 8-acetoxyoctan-1-al (7) was synthesized from 1,8-octanediol which is cheap and readily available.

The fluorescence intensity of khellin-dimethylfumarate C$_4$-cycloadduct (KDF) is very sensitive to temperature and to the nature of solvents, especially hydrogen-bonding ability. The fluorescence quantum yields of KDF in ethanol and isopentane at 77K are 0.73 and 0.54, respectively, both of which are much larger than the room temperature values. The phosphorescence lifetime is very long and decreases with decreasing the solvent polarity. The phosphorescence and fluorescence quantum yield ratio is very small and decreases with decreasing solvent polarity. The solvent relaxation plays an important role in the excited states of KDF. The internal conversion is a major decay process of the excited singlet state of KDF in all the solvents used at room temperature.

Kinetics and Mechanism of $N_2H_4-KBrO_3$ reaction in the presence of allyl alcohol have been studied. The pseudo-first order rate constant for gas evolution was found to be $10^{-4}{\sim}10^{-2}\;sec^{-1}\;at\;25.0{\pm}0.1^{\circ}C$, increasing with concentration of hydrogen ion. When concentrations of sulfuric acid and allyl alcohol are both sufficiently high, the following overall reaction explains experimental results reasonably well: $N_2H_4\;+\;BrO_3^-\;+\;H^+\;{\to}\;N_2\;+\;HOBr\;+\;2H_2O,\;CH_2\;=\;CHCH_2OH\;+\;HOBr\;{\to}\;CH_2-OHCHBrCH_2OH$. More complicated reaction mechanisms at lower acidity conditions have been contemplated.

Reaction of $Ir(ClO_4)(CO)(PPh_3)_2$ with trans-$C_6H_5CH$ = $CHCO_2C_2H_5$ produces a new cationic iridium(I) complex, [Ir (trans-$C_6H_5CH$ = $CHCO_2C_2H_5)(CO)(PPh_3)_2]ClO_4$ where trans-$C_6H_5CH$ = $CHCO_2C_2H_5$ seems to be coordinated through the carbonyl oxygen rather than through the $\pi$-system of the olefinic group according to the spectral data. It has been found that Ir$(ClO_4)(CO)(PPh_3)_2$ catalyzes the hydrogenation of $CH_2$ = $CHCO_2C_2H_5$, trans-$CH_3CH$ = $CHCO_2C_2H_5$ and trans-$C_6H_5CH$ = $CHCO_2C_2H_5$ to $CH_3CH_2CO_2C_2H_5$, $CH_3CH_2CH_2CO_2C_2H_5$ and $C_6H_5CH_2CH_2CO_2C_2H_5$, respectively at room temperature under the atmospheric pressure of hydrogen. The relative rates of the hydrogenation of the unsaturated esters are mostly understood in terms of steric reasons.

The isolated products from the reactions of $Rh(ClO_4)(CO)(PPh_3)_2$ (1) with CH_2$ = $CHCO_2C_2H_5$ (2) and trans-$CH_3CH$ = $CHCO_2C_2H_5$ (3) contain 80∼ 90% of $[Rh(CH_2 = CHCO_2C_2H_5)(CO)(PPh_3)_2]ClO_4$ (4) and [Rh(trans-$CH_3CH = CHCO_2C_2H_5(CO)(PPh_3)_2]ClO_4$ (5), respectively where 2 and 3 seem to be coordinated through the carbonyl oxygen. It has been found that complex 1 catalyzes the isomerization of $CH_2 = CH(CH_2)_8CO_2C_2H_5$ (6) to $CH_3(CH_2)_nCH = CH(CH_2)_{7-n}CO_2C_2H_5$ (n = 0∼7) under nitrogen at 25$^{\circ}C$. The isomerization of 6 is slower than that of $CH_2 = CH(CH_2)_9CH_3$ to $CH_3(CH_2)_nCH$ = $CH(CH_2)_{8-n}CH_3$ (n = 0∼8), which is understood in terms of the interactions between the carbonyl oxygen of 6 and the catalyst. It has been also observed that complex 1 catalyzes the hydrogenation of 2, 3, 6, trans-$C_6H_5CH = CHCO_2C_2H_5$ (7), $CH_3(CH_2)_7CH = CH(CH_2)_7CO_2C_2H_5$ (8) and $CH_2 = CH(CH_2)_9CH_3$ (9), and the isomerization (double bond migration) of 6 and 9 under hydrogen at 25$^{\circ}C$. The interactions between the carbonyl oxygen of the unsaturated esters and the catalyst affect the hydrogenation in such a way that the hydrogenation of the unsaturated esters becomes slower than that of simple olefins.

The reaction of (E)- or (Z)-1-alkenylmercuric chlorides with acrylic acid derivatives in the presence of 10 mol% of lithium trichloropalladate ($LiPdCl_3$) and an equimolar amount of cupric chloride, as a reoxidant for the palladium, in acetonitrile at room temperature gave the corresponding (E,E)- or (E,Z)-2,4-dienoic acid derivatives stereospecifically in moderate to good yields. The reaction of (E)- or (Z)-3-chloromercuripropenoic acid with olefins under the reaction condintion described above similarly gave good yields of (E,E)- or (Z,E)-2,4-dienoic acids stereospecifically. A side reaction, the homocoupling of alkenylmercuric chlorides, could be minimized by employing the condition described above. However, in the reaction of 3-chloromercuripropenoic acid with olefins under the present condition, the homocoupled side reaction product was not produced.