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Woodman, Timothy J., Schormann, Mark and Bochmann, Manfred 
ORCID: https://orcid.org/0000-0001-7736-5428
(2003)
Synthesis, characterization, and reactivity of ansa-bis(allyl) lanthanide complexes, a new class of single-component methyl methacrylate polymerization catalysts.
Organometallics, 22 (14).
pp. 2938-2943.
Abstract
The reaction of the dipotassium salt K2{3-(C3H3SiMe3-1)2SiMe2} with LnCl3 in THF leads to the formation of the new ansa-allyl lanthanate complexes [Ln{(?3-C3H3SiMe3)2SiMe2}2{µ-K(THF)}·nTHF]8 ( 1 , Ln = La, n = 0.5; 2 , Ln = Y, n = 1; 3 , Ln = Sc, n = 1). Reaction of K2{3-(C3H3SiMe3-1)2SiMe2} with NdI3(THF)3.5 affords THF-free [Nd{(?3-C3H3SiMe3)2SiMe2}2(µ-K)]8 ( 4 ). Treatment of SmI2(THF)2 with Li{3-(C3H3SiMe3-1)2SiMe2}/KOtBu resulted in the samarium(III) complex [Li(OEt2)4][Sm{(?3-C3H3SiMe3)2SiMe2}2] ( 5 ), albeit in small yield. Whereas the crystal structure of 1 shows a coordination polymer, with potassium bridging to allyl moieties of two neighboring lanthanide units and close K···CH3Si contacts, complex 5 consists of discrete ions. The complexes 1 - 5 are all found to be efficient catalysts for the polymerization of methyl methacrylate to high-molecular-weight polymers under a variety of conditions, with 2 at 0 °C giving extremely high turnovers of 86 400 mol of MMA (mol of Y)-1 h-1.
| Item Type: | Article |
|---|---|
| Faculty \ School: | Faculty of Science > School of Chemistry |
| UEA Research Groups: | Faculty of Science > Research Groups > Chemistry of Materials and Catalysis Faculty of Science > Research Groups > Chemistry of Light and Energy Faculty of Science > Research Groups > Synthetic Chemistry (former - to 2017) |
| Depositing User: | Rachel Smith |
| Date Deposited: | 02 Nov 2010 17:48 |
| Last Modified: | 07 Mar 2023 15:30 |
| URI: | https://ueaeprints.uea.ac.uk/id/eprint/10490 |
| DOI: | 10.1021/om0301334 |
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