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Thepolymerizationofole nsanddi-ole nsisoneofthemostimportanttargets inpolymerscience.Thisreviewarticledescribesrecentprogressinthis eldand deals with organo-transition metal complexes as polymerization catalysts. - cent developments in organometallic chemistry have prompted us to nd a precise description of the mechanism of propagation, chain transfer, and terminationstepsinthehomogeneouslymetal-assistedpolymerizationofole ns anddiole ns.Thus,thisdevelopmentprovidesanideafordesigninganycatalyst systems that are of interest in industry. Recently,the agostic interactionofalkylgroup(s)ontransitionmetalshas emerged as highly basic and new concept and is found to be important in understandingthemechanismofthemetal-catalyzedhomogeneousoligomer- ation and polymerization of a-ole ns. Early transition metal alkyl complexes generallyhavepartiallyionicM-C bondsandshowa-agostichydrogeninter- tion that somewhat stabilizes the catalytically active species by providing el- tronsatavacantsite onthe metal.Thisisinsharp contrasttothefactthatlate transition metal alkyl complexes show mainly b-agostic hydrogen interaction that causes the hydrogen transfer easily through b-hydrogen elimination and reductive elimination, and that gives rise to the oligomerization of ole ns. Organometalliccomplexesoftheearlyandlatetransitionmetalshavebeenused as catalysts for ole n oligomerization and polymerization. The mechanism involved in these catalyst systems depends very much upon the kind of metal centersaswellastheirco-ligands,andthusthedi?erentmechanismswhichcan bedistinguishedbydetailedinvestigationsshouldbeassumedforearlyandlate transition metal catalysts. In this contribution, we review the mechanism of polymerization and oligomerization involving early transition metals, taking as our basis recent resultsinadvancedorganometallicchemistry.Firstofall,somerecentexamples of the previous reviews concerning the Ziegler-Natta polymerization are cited [1-10]. Then, relevant new reports are surveyed in a systematic fashion.
Organic Synthesis via Organometallics is an interdisciplinary project sponsored by the Volkswagen Stiftung to stimulate research and discussion of advances in the field. To improve international communication , leading experts are invited to regular symposia. In this volume, 17 lectures presented at the second symposium in Wurzburg, October 1988, are collected. From the topics covered it complements the previous volume, edited by A. de Meijere and H. tom Dieck.
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