Issue 42, 2018

Selective and catalytic carbon dioxide and heteroallene activation mediated by cerium N-heterocyclic carbene complexes

Abstract

A series of rare earth complexes of the form Ln(LR)3 supported by bidentate ortho-aryloxide–NHC ligands are reported (LR = 2-O-3,5-tBu2-C6H2(1-C{N(CH)2N(R)})); R = iPr, tBu, Mes; Ln = Ce, Sm, Eu). The cerium complexes cleanly and quantitatively insert carbon dioxide exclusively into all three cerium carbene bonds, forming Ce(LR·CO2)3. The insertion is reversible only for the mesityl-substituted complex Ce(LMes)3. Analysis of the capacity of Ce(LR)3 to insert a range of heteroallenes that are isoelectronic with CO2 reveals the solvent and ligand size dependence of the selectivity. This is important because only the complexes capable of reversible CO2-insertion are competent catalysts for catalytic conversions of CO2. Preliminary studies show that only Ce(LMes·CO2)3 catalyses the formation of propylene carbonate from propylene oxide under 1 atm of CO2 pressure. The mono-ligand complexes can be isolated from reactions using LiCe(NiPr2)4 as a starting material; LiBr adducts [Ce(LR)(NiPr2)Br·LiBr(THF)]2 (R = Me, iPr) are reported, along with a hexanuclear N-heterocyclic dicarbene [Li2Ce3(OArCMe–H)3(NiPr2)5(THF)2]2 by-product. The analogous para-aryloxide–NHC proligand (p-LMes = 4-O-2,6-tBu2-C6H2(1-C{N(CH)2NMes}))) has been made for comparison, but the rare earth tris-ligand complexes Ln(p-LMes)3(THF)2 (Ln = Y, Ce) are too reactive for straightforward Lewis pair separated chemistry to be usefully carried out.

Graphical abstract: Selective and catalytic carbon dioxide and heteroallene activation mediated by cerium N-heterocyclic carbene complexes

Supplementary files

Article information

Article type
Edge Article
Submitted
26 7 2018
Accepted
05 9 2018
First published
10 9 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2018,9, 8035-8045

Selective and catalytic carbon dioxide and heteroallene activation mediated by cerium N-heterocyclic carbene complexes

P. L. Arnold, R. W. F. Kerr, C. Weetman, S. R. Docherty, J. Rieb, F. L. Cruickshank, K. Wang, C. Jandl, M. W. McMullon, A. Pöthig, F. E. Kühn and A. D. Smith, Chem. Sci., 2018, 9, 8035 DOI: 10.1039/C8SC03312A

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