Date of Award

5-2002

Degree Type

Dissertation

Degree Name

Doctor of Philosophy

Major

Chemistry

Major Professor

Craig Eliot Barnes

Committee Members

George K. Schweitzer, Mark D. Dadmun, Engin Serpersu

Abstract

Three metallocene and half-sandwich Group 4 complexes of cuboctameric

spherosilicate (Si8O20(TiCp2Cl)8, Si8O20(ZrCp2Cl)8, and Si8O20(TiCp*Cl2)8) were successfully prepared by the exchange reaction of Group 4 metal chlorides with the spherosilicate starting material, Si8O20(SnMe3)8. These complexes were found to be catalytically active in olefin polymerization. Their preparative reactions clearly demonstrate a synthetically useful route towards many other derivatives of spherosilicate through the Si8O20(SnMe3)8 starting material. A new synthesis of the key precursor, octa(trimethyltin) cuboctameric spherosilicate Si8O20(SnMe3)8, was developed. It was found that most of the waters of hydration of the initial hydrate ([NMe4][Si8O20] @ n H2O, = 60! 70) could be removed by heating to 90 ! 100 °C. This “dehydrated” material proved to be synthetically useful and could be exhaustively silylated and stannylated in good to fair yields. The structures of Si8O20(SnMe3)8, Si8O20(SiMe3)8, and Si8O20(TiCp2Cl)8 are reported.

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