γ-Agostic interactions stabilize the propagating species in the vinyl addition polymerization of norbornene

Marc D. Walter; Peter S. White; Maurice Brookhart

doi:10.1039/B916457J

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Chemical Communications

Issue 42, 2009

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γ-Agostic interactions stabilize the propagating species in the vinyl addition polymerization of norbornene

Marc D. Walter , Peter S. White and Maurice Brookhart

Chem. Commun., 2009, 6361-6363

DOI: 10.1039/B916457J
Received 10 Aug 2009, Accepted 03 Sep 2009
First published on the web 28 Sep 2009
This article is part of the collection: Selective Catalysis for Organic Synthesis

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Abstract
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Cationic [(tmeda)Pd(OEt₂)(Me)][B(Ar_F)₄] was synthesized by protonation of (tmeda)PdMe₂ and allowed for the first time the nature of the propagating species in the vinyl addition polymerization of norbornene to be discerned. In this system γ-agostic interactions stabilize the propagating species and permit stepwise monomer insertions to be observed by ¹H NMR spectroscopy. This and earlier studies provide a new proposal for the propagating species in ligand-less late transition metal-catalyzed norbornene polymerizations.

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Chemical Communications

γ-Agostic interactions stabilize the propagating species in the vinyl addition polymerization of norbornene

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