DEVELOPMENT OF NEW CATALYSIS REACTIONS WITH METAL SALTS OF FLUORINATED WEAKLY COORDINATED ANIONS

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THIS IS A BASIC RESEARCH TO PREPARE ALKALI METAL AND ALKALI-EARTH METAL SALTS OF VARIOUS FLUORINATED WEAKLY COORDINATING ANIONS AND TO INVESTIGATE SOME NEW CARBON-CARBON BOND FORMATION REACTIONS WHICH CAN BE PROMOTED IN CATALYTIC WAYS BY ELECTROPHILIC LITHIUM IONS EXTREMELY ACTIVATED BY THE COUNTER ANIONS IN WEAKLY COORDINATING ORGANIC SOLVENTS. THE EFFECTS OF METAL IONS AND THE STRUCTURE OF WEAKLY COORDINATING ANIONS ON THE CATALYTIC ACTIVITY AND THE MECHANISM OF THE REACTIONS ARE INVESTIGATED BY EXPERIMENTAL AND COMPUTATIONAL METHODS.COMPUTATIONAL STUDY: THE COORDINATING ABILITY OF VARIOUS WEAKLY COORDINATING ANIONS WAS QUANTITATIVELY EVALUATED AS FOLLOWS BY GAUSSIAN 98 AND SPARTAN WITH AB INITIO AND DFT METHODS; 1) THE RELATIONSHIP BETWEEN GAS-PHASE ACIDITY AND CALCULATED ACIDITY OF NEUTRAL BROENSTED-TYPE SUPERACIDS; 2) THE EFFECT OF COUNTER ANIONS ON THE ELECTROPHILICITY OF LITHIUM IONS TOWARD VARIOUS ORGANIC COMPOUNDS; 3) TRANSITION STATE STRUCTURES OF DIELS -ALDER REACTION AND VALENCE- ISOMERIZATION OF QUADRICYCLANE PROMOTED BY LITHIUM IONS.EXPERIMENTAL STUDY: VARIOUS/LITHIUM AND SODIUM SALTS OF FLUORINATED WEAKLY COORDINATING ANIONS SUCH AS TETRAARYLBORATE ANIONS, IMIDE ANIONS, METHIDE ANIONS, AND ALUMINATE ANIONS ARE NEWLY PREPARED. HALOCHROMIZM OF TRITYL CHLORIDE AND TRITYL ALCOHOLE AND DIELS-ALDER REACTIONS OF CYCLOPENTADIENE AND VALENCE- ISOMERIZATION REACTIONS OF QUADRICYCLANE PRPMOTED BY VARIOUS LITHIUM SALTS IN WEAKLY COORDINATING ORGANIC SOLVENTS ARE INVESTIGATED BY KINETIC METHODS TO EVALUATE THE LEWIS ACIDITY OF LITHIUM IONS IN SOLUTION.