Goldilocks Effect of a Distal Substituent on Living Ziegler−Natta Polymerization Activity and Stereoselectivity within a Class of Zirconium Amidinate-Based Initiators
Citations Over TimeTop 10% of 2004 papers
Abstract
A new series of cationic zirconium amidinates, [(η5-C5Me5)ZrMe{N(Et)C(R3)N(tBu)}][B(C6F5)4] (R3 = Me, H, Ph, and tBu) (1a−d), were synthesized and their ability to function as initiators for the stereoselective living Ziegler−Natta polymerization of 1-hexene evaluated. Whereas 1a is highly active for the isospecific living polymerization of 1-hexene as previously reported, polymerizations conducted with 1b and 1c both display a significant loss of stereocontrol, and in the case of 1b, the polymerization is no longer living. Further, 1d was found to be inactive for polymerization. The Golidlocks effect observed for the distal R3 substituent in this series, i.e., 1b “too small”, 1c “too large”, 1a “just right”, appears to be steric in origin. Solution and solid state structural studies suggest, however, that two different mechanisms are most likely operative for the loss of stereocontrol observed for 1b and 1c: a low barrier to metal-centered epimerization in the case of 1b and a lack of steric discrimination at the metal center for olefin binding in the case of 1c.
Related Papers
- → Reductive Formation of Isospecific Ti Dinuclear Species on a MgCl2 (110) Surface in Heterogeneous Ziegler‐Natta Catalysts(2008)57 cited
- → Models for the stereospecificity in homogeneous and heterogeneous Ziegler-Natta polymerizations(1991)76 cited
- → Study of Dimethoxysilacycloalkanes as External Donors in Ziegler-Natta Stereospecific Propylene Polymerisation(2005)17 cited
- → Stereospecific synthesis and stereochemical structure confirmation of dumetorine(1987)16 cited
- → New stereospecific routes to both epimers of 2-methyl-3-oxo- and 3-methyl-2-oxo-steroids via 2-lithio-1,3-dithian–epoxide reactions(1970)5 cited