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The study was conducted to examine the geometry and electronic structure of group 10 and 11 metal carbonyl cations,[M(CO)(sub n)](super x+) (M(super x+)=Ni(super 2+) Pd(super 2+), Pt(super 2+), Cu(super +), Ag(super +), Au(super x); n = 1-4) by the hybrid density functional method (B3LYP) and the coupled cluster method (CCSD(T)). The results reveal that the virbational frequencies V(CO) were higher by 100-165 cm(super -1) 45-115 cm(super -1) for group 11 metal complexes than that for free CO(2143 cm(super -1).

A platinum carbonyl compound was prepared by NMR, IR, Raman and EXAFS spectroscopy.

Results demonstrate that the NO(sub)2(sup)+ nitration of an aromatic compound 1,8-dimethylnaphthalene follows an electrophilic as well as a direct charge-transfer process. The other reactions occurring during the process are ipso attack of NO(sub)2(sup)+, the 1,2-shift of the NO(sub)2 group, and an alternative charge-transfer reaction.

The carbonylation of olefins by the cationic metal carbonyl catalysts is described. Research demonstrates rhodium carbonyl catalyst mediates the reaction of olefins with carbon monoxide to produce tertiary carboxylic acids at atmospheric pressure and room temperature.

A new palladium carbonyl catalyst in concentrated H2SO4 is described with which olefins and alcohols react with CO to generate tertiary carboxylic acids in high yields at atmospheric pressure and room temperature. The formation of a new Pd(I) carbonyl complex without bridging CO ligands was observed. The catalytic nature of the palladium carbonyl catalyst supports the proposed reaction mechanism involving an olefin-metal-CO complex as an intermediate for the catalytic carbonylation of olefins and alcohols in strongly acidic solution.

Kinetic and regioselectivity studies were conducted on the intracomplex reaction in Gattermann-Koch formylation in superacids. The findings indicate the presence of intracomplex reaction via a third-order rate equation. Furthermore, high para regioselectivity results from intracomplex reaction. Regioselectivity comparison between Gattermann-Koch formylation and Friedel-Crafts formylation showed that regioselectivity trends are not reflective of the nature of the electrophile but the reaction pathway.

The synthesis and characterization of a new gold catalyst, (Au(CO)n)+ (n = 12), are described. The scheme involves the reduction of gold(III) oxide by CO to form (Au(CO)n)+ in one step in concentrated H2SO4 solution. The nonclassical gold(I) catalyst has been applied to the reaction of olefins with CO to form tert-carboxylic acids, giving good yields at room temperature and atmospheric pressure.

Catalytic coupling reaction of naphthalene derivatives and NaNO2 with CF3SO3H leads to respective 1,1'-binaphthyl derivatives in air. In the reaction, CH3CN acts as a catalyst and CF3SO3H as a Bronsted acid. The presence of a strong Bronsted acid induces the formation of binaphthyl derivatives rather than the nitro compounds. Acid promotes the formation of NO+ and restriction of nitration. The effect of steric hindrance influence the production and regioselectivity of the coupling reaction.

Gattermann-Koch reactions, or acid-catalyzed formylations of aromatics, are now possible under atmospheric carbon monoxide (CO) pressure. With fluoro- sulfonic acid (HSO3F) and antimony pentafluoride (SbF5) as catalysts, CHO- addition takes place before and alongside sulfonation to yield formyl and sulfonyl compounds. Alkylbenzene substrates yield a new range of products: alkylbenzaldehydes, alkylbenzenesulfonyl fluorides and bis(alkylphenyl)- sulfones. The ratio of formyl to sulfonyl products is a direct function of the acidity of the reaction medium.

Aromatic compounds react with HSO3F at 0-50 degrees C in the presence of antimony pentafluoride (SbF5) to form arylsulfonyl fluorides and diaryl sulfones in high yields. The sulfone/fluoride ratio increases as SbF5 levels are raised, the required amount of which decreases with increasing reactivity of the aryl compound. Polyalkylbenzenes, on the other hnad, favor the formation of fluorides. The highest yield for diphenyl sulfone is achieved when the SbF5/benzene ratio is 1:1.5. An interesting revelation is that diaryl sulfone is formed via the condensation of benzene with the initial product, benezenesulfonic acid.

I discovered novel copper and silver carbonyl catalysts while at the National Institute of Advanced Industrial Science and Technology. The energy saving synthesis of tert-carboxylic acids was developed using the carbonylation reaction of olefins or alcohols using these novel copper or silver carbonyl catalysts under atmospheric pressure and at room temperature. After retiring from the institute, I was involved in efforts to improve women's status in natural science, technology, engineering, and mathematics. I worked for the gender equality committee of the Chemical Society of Japan and the Japan Inter-Society Liaison Association Committee for Promoting Equal Participation of Men and Women in Science and Engineering, which sent recommendations to the government on how to realize a society with gender equality. The government accepted our recommendations, and the numerical target for female researchers was written into the 3rd Science and Technology Basic Plan in 2006. Based on the plan, the Ministry of Education, Culture, Sports, Science and Technology started programs to aid universities in increasing the percentage of female researchers from 2006. [ABSTRACT FROM AUTHOR]

The first example of the homoleptic, dinuclear, cationic metal carbonyl catalyst in concentrated sulfuric acid, with which olefins react with CO to produce tertiary carboxylic acids in high yields at atmospheric pressure and room temperature, is reported. It was observed that the cis-Pt-(CO)2 square+9solv) has a very low catalytic activity for the carbonylation of olefins in strong acids.