Details zur Publikation

Kategorie Textpublikation
Referenztyp Buchkapitel
DOI 10.1021/bk-2002-0822.ch006
Titel (primär) Electronic and steric design of novel group 13 Lewis acids and their synthesis via metal-tin exchange reaction (1): Toward the ideal olefin polymerization catalyst
Titel (sekundär) Group 13 Chemistry. From Fundamentals to Application
Autor Eisch, J.J.; Otieno, P.O.; Mackenzie, K. ORCID logo ; Kotowicz, B.W.
Herausgeber Shapiro, P.J.; Atwood, D.A.
Quelle ACS Symposium Series
Erscheinungsjahr 2002
Department TUCHEM; SAN
Band/Volume 822
Seite von 88
Seite bis 103
Sprache englisch
Abstract

Group 13 Lewis acids have long played a leading role as catalysts in organic synthesis, extending from the discovery of AlCl3-catalysis by Friedel and Crafts in 1877 through the Aufbau-synthesis of unsolvated aluminum alkyls from ethylene by Ziegler in 1952 and culminating in the discovery of poly(methylaluminoxane) (MAO) cocatalysis of olefin polymerization by Sinn and Kaminsky in 1976. In our current work we present how electronic and steric contributions of the ligands attached to the particular Group 13 metal can modulate the resultant Lewis acidity. The inherent Lewis acidity of the Group 13 metal center itself is further dependent upon the extent that its available np(z)-orbital might interact with adjacent unshared or pi-electrons of the ligand system. In order to evaluate the effect of such electronic factors on their Lewis acidity, both a series of bidentate Group 13 organoboron and organoaluminum candidate acids, as well as their antiaromatic metallole analogs, have been synthesized by exchange reactions between the corresponding organotin compound and the appropriate metal halide. Their Lewis acidity has been evaluated based upon their efficacy as a cocatalyst with titanocene(IV) methyl chloride or titanocene(IV) dichloride in effecting the polymerization of ethylene.

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Eisch, J.J., Otieno, P.O., Mackenzie, K., Kotowicz, B.W. (2002):
Electronic and steric design of novel group 13 Lewis acids and their synthesis via metal-tin exchange reaction (1): Toward the ideal olefin polymerization catalyst
In: Shapiro, P.J., Atwood, D.A. (eds.)
Group 13 Chemistry. From Fundamentals to Application
ACS Sym. Ser. 822
American Chemical Society (ACS), Washington, DC, p. 88 - 103 10.1021/bk-2002-0822.ch006