Combining alkali metals and zinc to harness heterometallic cooperativity in cyclic ester ring-opening polymerisation.

Chemical Science
Weronika GruszkaJennifer A Garden

Abstract

Heterometallic cooperativity is an emerging strategy to elevate polymerisation catalyst performance. Here, we report the first heterotrimetallic Na/Zn2 and K/Zn2 complexes supported by a ProPhenol ligand, which deliver "best of both" in cyclic ester ring-opening polymerisation, combining the outstanding activity (Na/K) and good control (Zn2) of homometallic analogues. Detailed NMR studies and density-functional theory calculations suggest that the Na/Zn2 and K/Zn2 complexes retain their heterometallic structures in the solution-state. To the best of our knowledge, the K/Zn2 analogue is the most active heterometallic catalyst reported for rac-lactide polymerisation (kobs = 1.7 × 10-2 s-1), giving activities five times faster than the Na/Zn2 complex. These versatile catalysts also display outstanding performance in ε-caprolatone and δ-valerolactone ring-opening polymerisation. These studies provide underpinning methodologies for future heterometallic polymerisation catalyst design, both in cyclic ester polymerisation and other ring-opening (co)polymerisation reactions.

References

Jul 18, 2001·Journal of the American Chemical Society·B M ChamberlainG W Coates
Oct 7, 2004·Macromolecular Bioscience·Rafael AurasSusan Selke
Oct 14, 2005·Journal of the American Chemical Society·Charlotte K WilliamsWilliam B Tolman
Nov 10, 2005·Chemical Reviews·Chang-Sik Ha, Joseph A Gardella
Aug 28, 2007·Chemical Society Reviews·Charlotte K Williams
Apr 8, 2009·Accounts of Chemical Research·Robert E Mulvey
Jan 30, 2010·Chemical Society Reviews·Matthew J Stanford, Andrew P Dove
Jun 22, 2013·Nature Chemistry·K Cory Macleod, Patrick L Holland
Dec 25, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Claire Wombwell, Erwin Reisner
Jul 31, 2014·Accounts of Chemical Research·Jennifer P McInnisTobin J Marks
Aug 12, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Bijja RajashekharVenkatachalam Ramkumar

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Citations

Jun 2, 2021·Nature Communications·Weronika Gruszka, Jennifer A Garden
Nov 10, 2021·Chemical Communications : Chem Comm·Chloe A BakerNicholas J Long

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Methods Mentioned

BETA
NMR
X-ray

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