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Scheme 1. Proposed catalytic cycle for the Ni-catalyzed acrylate formation. The first
step (I) involves the oxidative coupling of ethene and CO2 on a Ni0 phosphine com-
plex. This is followed by the coordination of the Lewis acid (Li+) to the carboxylate
moiety of the lactone ring to facilitate NiÀO bond dissociation (II). Upon (partial) dis-
sociation, b-H elimination can occur (III) with subsequent release of lithium acrylate
and regeneration of the active Ni0 species by the base (IV).
[9] R. Fischer, J. Langer, A. Malassa, D. Walther, H. Gorls, G. Vaugh-
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with a magnetic stirrer bar, a solution of [Ni(cod)2] (0.05 mmol) and
ligand (0.05 mmol) in PhCl (2 mL) was added. The vial was closed
with a screw cap with a PTFE/silicon septum, and to each vial Et3N
(2.5 mmol) was added via syringe. The vials were transferred to
a 75 mL stainless steel autoclave and the septum punctured with
a small needle. The autoclave was closed and pressurized to the re-
quired ethene pressure. After stirring for 2.5 h at room tempera-
ture, the autoclave was pressurized with additional CO2 to the re-
quired pressure. The autoclave was heated to 508C for 72 h. After
cooling to ambient temperature, the pressure was gradually re-
leased from the autoclave. The vials were removed from the auto-
clave and to each vial, 1000 mL D2O with 0.25 mmol LiOAc·2H2O
was added as internal standard. After vigorous stirring for 30 min,
the combined phases were filtered over cotton wool and the D2O
layer was separated from the organic phase. The turn over number
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was determined by H NMR spectroscopy of the D2O layer.
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Acknowledgements
The authors gratefully acknowledge financial support by CREA-
VIS - Science to Business, Evonik Industries AG.
Keywords: acrylates
·
carbon dioxide
·
homogeneous
catalysis · Lewis acids · lithium · sustainable chemistry
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Received: June 23, 2014
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