SVIBOR - Project code: 1-07-185

MINISTRY OF SCIENCE AND TECHNOLOGY

Strossmayerov trg 4, HR - 10000 ZAGREB
tel.: +385 1 459 44 44, fax: +385 1 459 44 69
E-mail: ured@znanost.hr

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Project code: 1-07-185

Structure and reactions of carbocations

Main researcher: SUNKO, DIONIS (45491)

Assistants

VANČIK, HRVOJ (91661)
MIHALIĆ, ZLATKO (41775)
MESIĆ, MILAN (159405)
PETROVIĆ-PEROKOVIĆ, VESNA (900531)

Type of research: basic
Duration from: 01/01/91. to 12/31/93.

Papers on project (total): 13
Papers on project quoted in Current Contents: 10

Institution name: Prirodoslovno-matematički fakultet, Prirodoslovni odjeli, Zagreb (119)
Department/Institute: Laboratory of organic chemistry and biochemistry
Address: Strossmayerov trg 14
City: 10000 - Zagreb, Croatia

Communication: Phone: 385 (0)41 432-580; Phone: 385 (0)41 434-770; Fax: 385 (0)41 432-526; E-mail: desunko at olimp.irb.hr; E-mail: mihalic at srcapp.srce.hr

Summary: The recently developed matrix isolation technique of carbocationic intermediates enables the continuation of our studies of structure and reactivity of these short-lived species by a combination of spectroscopic, kinetic and quantum-mechanical methods. Of special interest are studies of long-range interactions, molecular rearrangements and isotope effects as well as the comparison of experimental results obtained by the application of the matrix isolation technique with those of solvolytic studies and theoretical calculations at the semiempirical and ab initio levels. The mechanisms of biomimetic cyclizations are studied under micellar conditions which mimic enzymatically catalyzed biosynthetic processes such as those operative in the biogenesis of terpenes and steroids.

Keywords: carbocations, matrix isolation, solvolysis, isotope effects, molecular rearrangements, long range effects, spectroscopy, quantum-chemical calculations, biomimetic cyclizations, micellar systems

Research goals: 1. To investigate the stability of different carbocations and similar intermediates in super acidic medium. 2. To work out the most convenient method for their isolation. 3. To investigate their activity by spectroscopically measuring the electronic effects responsible for chemical behaviour. 4. To determine vibrational structures of these cations and/or similar species. 5. To study the relationship between vibrational structure and chemical reactivity in cases when these ions and similar species are perturbed by strong chemical agens. 6. To study the mechanisms of biomimetic cyclizations under micellar conditions that mimics enzymatically catalyzed biosynthetic processes such as those operative in the biogenesis of terpenes and steroids.

Other information about the project.


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